Fungicidal 1,2,3 triazole derivatives

ABSTRACT

A compound of formula (I):, where A is an ortho-substituted ring selected from a number of specified rings; R 1  is halogen, cyano, nitro, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy or C 1-4  haloalkoxy or optionally substituted C 2-4  alkenyl, optionally substituted C 2-4  alkynyl or optionally substituted SO2(C 1-4  alkyl) (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy); R 2  is C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy(C 1-4 )alkyl or C 1-4  alkylthio(C 1-4 )alkyl or [optionally substituted aryl](C 1-4 )alkyl- or [optionally substituted aryl]oxy(C 1-4 )alkyl (where the optionally substituted aryl moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy); R 3  is hydrogen, CH 2 C≡CR 4 , CH 2 CR 4 ═C(H)R 4 , CH═C═CH 2  or COR 5  or optionally substituted C 1-4  alkyl, optionally substituted C 1-4  alkoxy or optionally substituted (C 1-4 )alkylC(═O)O (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen and C 1-4  alkoxy, C 1-4  alkyl, C 1-2  haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl and ethylsulfonyl); each R 4  is, independently, hydrogen, halogen, C 1-4  alkyl, C 1-4  haloalkyl, C 1-4  alkoxy or C 1-4  alkoxy(C 1-4 )alkyl; and R 5  is hydrogen or optionally substituted C 1-6  alkyl, optionally substituted C 1-4  alkoxy, optionally substituted C 1-4  alkoxy(C 1-4 )alkyl, optionally substituted C 1-4  alkylthio(C 1-4 )alkyl or optionally substituted aryl (where the optionally substituted moieties may each have up to 3 substituents, each independently selected from halogen, C 1-6  alkoxy, C 1-6  haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl).

This application is a 371 of International Application No.PCT/EP2003/009111 filed Aug. 18, 2003, which claims priority to GB0219612.9, filed Aug. 22, 2002, and GB 0310464.3 filed May 7, 2003, thecontents of which are incorporated herein by reference.

The present invention relates to novel 1,2,3-triazole derivatives whichhave microbiocidal activity, in particular fungicidal activity. Theinvention also relates to novel intermediates used in the preparation ofthese compounds, to agrochemical compositions which comprise at leastone of the novel compounds as active ingredient and to the use of theactive ingredients or compositions in agriculture or horticulture forcontrolling or preventing infestation of plants by phytopathogenicmicroorganisms, preferably fungi.

The present invention provides a compound of formula (I):

where A is an ortho-substituted ring selected from formulae (A1) to(A22);

Q is a single or a double bond; X is O, N(R¹⁸), S or(CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n); R¹ is halogen, cyano, nitro, C₁₋₄alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy or optionallysubstituted C₂₋₄ alkenyl, optionally substituted C₂₋₄ alkynyl oroptionally substituted SO₂(C₁₋₄)alkyl (where the optionally substitutedmoieties may each have up to 3 substituents, each independently selectedfrom halogen and C₁₋₄ alkoxy); R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄alkoxy(C₁₋₄)alkyl or C₁₋₄ alkylthio(C₁₋₄)alkyl or [optionallysubstituted aryl](C₁₋₄)alkyl- or [optionally substitutedaryl]oxy(C₁₋₄)alkyl- (where the optionally substituted aryl moieties mayeach have up to 3 substituents, each independently selected from halogenand C₁₋₄ alkoxy); R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ orCOR⁵ or optionally substituted C₁₋₄ alkyl, optionally substituted C₁₋₄alkoxy or optionally substituted (C₁₋₄)alkylC(═O)O (where the optionallysubstituted moieties may each have up to 3 substituents, eachindependently selected from halogen, C₁₋₄ alkoxy, C₁₋₄ alkyl, C₁₋₂haloalkoxy, hydroxy, cyano, carboxyl, methoxycarbonyl, ethoxycarbonyl,methylsulfonyl and ethylsulfonyl); each R⁴ is, independently, hydrogen,halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy or C₁₋₄alkoxy(C₁₋₄)alkyl; R⁵ is hydrogen or optionally substituted C₁₋₆ alkyl,optionally substituted C₁₋₄ alkoxy, optionally substituted C₁₋₄alkoxy(C₁₋₄)alkyl, optionally substituted C₁₋₄ alkylthio(C₁₋₄)alkyl oroptionally substituted aryl (where the optionally substituted moietiesmay each have up to 3 substituents, each independently selected fromhalogen, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, cyano, hydroxy, methoxycarbonyland ethoxycarbonyl); R⁶ is phenyl [optionally substituted by up to 3substituents, each independently selected from halogen, cyano, nitro,C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄haloalkylthio, C(H)═N—OH, C(H)═N—O(C₁₋₆ alkyl), C(C₁₋₆ alkyl)═N—OH,C(C₁₋₆ alkyl)═N—O—(C₁₋₆ alkyl), (Z)_(p)C≡CR²⁵ and (Z)_(p)CR²⁸═CR²⁶R²⁷],a 5-6 membered heterocyclic ring [in which the ring contains 1 to 3heteroatoms (each independently chosen from oxygen, sulphur andnitrogen) and the ring is optionally substituted by up to 3substituents, each independently selected from halogen, cyano, nitro,C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C(H)═N—O—(C₁₋₆alkyl) and C(C₁₋₆ alkyl)═N—O—(C₁₋₆ alkyl)], C₃₋₁₂ alkyl [optionallysubstituted by up to 6 substituents, each independently selected fromhalogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—C₁₋₄ alkyl, ═N—OH,═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionally substituted by upto 3 substituents, each independently selected from C₁₋₄ alkyl, halogen,C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and C₄₋₈ cycloalkenyl (itselfoptionally substituted by up to 3 substituents, each independentlyselected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy)],C₂₋₁₂ alkenyl [optionally substituted by up to 6 substituents, eachindependently selected from halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl,COO—(C₁₋₄ alkyl), ═N—OH, ═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itselfoptionally substituted by up to 3 substituents, each independentlyselected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) andC₄₋₈ cycloalkenyl (itself optionally substituted by up to 3substituents, each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄alkoxy and C₁₋₄ haloalkoxy)], C₂₋₁₂ alkynyl [optionally substituted byup to 6 substituents, each independently selected from halogen, cyano,C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—C₁₋₄ alkyl, ═N—OH, ═N—O—(C₁₋₄ alkyl),C₃₋₈ cycloalkyl (itself optionally substituted by up to 3 substituents,each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy andC₁₋₄ haloalkoxy), Si(CH₃)₃ and C₄₋₈ cycloalkenyl (itself optionallysubstituted by up to 3 substituents, each independently selected fromC₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy)], C₃₋₈ cycloalkyl[optionally substituted by up to 3 substituents, each independentlyselected from halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄haloalkoxy, C₁₋₄ thioalkyl, C₃₋₆ cycloalkyl (itself optionallysubstituted by up to 3 substituents, each independently selected fromC₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy) and phenyl (itselfoptionally substituted by up to five independently selected halogenatoms)], C₄₋₈ cycloalkenyl [optionally substituted by up to 3substituents, each independently selected from halogen, C₁₋₄ alkyl, C₁₋₄haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₃₋₆ cycloalkyl(itself optionally substituted by up to 3 substituents, eachindependently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄haloalkoxy) and phenyl (itself optionally substituted by up to fiveindependently selected halogen atoms)], C₆₋₁₂ bicycloalkyl [optionallysubstituted by up to 3 substituents, each independently selected fromhalogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl] or an aliphatic, saturated orunsaturated group [in which the group contains three to thirteen carbonatoms and at least one silicon atom and, optionally, one to threeheteroatoms, each independently selected from oxygen, nitrogen andsulphur, and the group is optionally substituted by up to fourindependently selected halogen atoms]; R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹² areeach, independently, hydrogen, halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl or C₁₋₄thiohaloalkyl; R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each, independently,hydrogen, halogen, C₁₋₄ alkyl, C(O)CH₃, C₁₋₄ haloalkyl, C₁₋₄ alkoxy,C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₁₋₄ thiohaloalkyl, hydroxymethyl orC₁₋₄ alkoxymethyl; R¹⁸ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl,formyl, C(═O)C₁₋₄ alkyl (optionally substituted by halogen orC₁₋₄-alkoxy) or C(═O)O—C₁₋₆ alkyl (optionally substituted by halogen,C₁₋₄ alkoxy or CN); R¹⁹, R²⁰, R²¹, R²², R²³ and R²⁴ are each,independently, C₁₋₆ alkyl, C₁₋₆ alkenyl [both optionally substituted byhalogen, hydroxy, ═O, C₁₋₄ alkoxy, O—C(O)—C₁₋₄ alkyl, aryl or a 3-7membered carbocyclic ring (itself optionally substituted by up to threemethyl groups)], a 3-7 membered carbocyclic ring (optionally substitutedby up to three methyl groups and optionally containing one heteroatomselected from nitrogen and oxygen), hydrogen, halogen, hydroxy or C₁₋₄alkoxy; or R¹⁹R²⁰ together with the carbon atom to which they areattached form a carbonyl-group, a 3-5 membered carbocyclic ring(optionally substituted by up to three methyl groups), C₁₋₆ alkylidene(optionally substituted by up to three methyl groups) or C₃₋₆cycloalkylidene (optionally substituted by up to three methyl groups);R²⁵ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄ haloalkoxy(C₁₋₄)alkyl or Si(C₁₋₄ alkyl)₃; R²⁶and R²⁷ are each, independently, hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄haloalkyl; R²⁸ is hydrogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl; m is 0 or 1; nis 0 or 1; p is 0 or 1; and Z is C₁₋₄ alkylene.

Halogen is fluoro, chloro, bromo or iodo.

Each alkyl moiety is a straight or branched chain and is, for example,methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl,sec-butyl, iso-butyl, tert-butyl, neo-pentyl, n-heptyl,1,3-dimethylbutyl, 1,3-dimethylpentyl, 1-methyl-3-ethyl-butyl or1,3,3-trimethylbutyl.

Haloalkyl moieties are alkyl moieties which are substituted by one ormore of the same or different halogen atoms and are, for example, CF₃,CF₂Cl, CHF₂, CH₂F, CCl₃, CF₃CH₂, CHF₂CH₂, CH₂FCH₂, CH₃CHF or CH₃CF₂.

Alkenyl and alkynyl moieties can be in the form of straight or branchedchains. The alkenyl moieties, where appropriate, can be of either the(E)- or (Z)-configuration. Examples are vinyl, allyl, ethynyl andpropargyl.

Alkylidene moieties can be in the form of straight or branched chains.Alkylidene includes methylidene [CH₂═C], ethylidene [CH₃C(H)═C],n-propylidene, i-propylidene [(CH₃)₂C═C], n-butylidene, i-butylidene,2-butylidene, n-pentylidene, i-pentylidene, neo-pentylidene,2-pentylidene, n-hexylidene, 2-hexylidene, 3-hexylidene, i-hexylideneand neo-hexylidene.

Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl and cyclooctyl.

Cycloalkenyl includes cyclobutenyl, cyclopentenyl, cyclohexenyl andcycloheptenyl.

Cycloalkylidene includes cyclopropylidene [c(C₃H₄)═C], cyclobutylidene,cyclopentylidene and cyclohexylidene.

Bicycloalkyl includes bicyclo[1,1,1]pentyl, bicyclo[2,1,1]hexyl,bicyclo[2,2,1]heptyl, bicyclo[2,2,2]octyl, bicyclo[3,2,1]octyl andbicyclo[3,2,2]nonyl.

Aryl includes phenyl, naphthyl, anthracyl, fluorenyl and indanyl but ispreferably phenyl.

In one aspect of the invention, A is as defined above provided that itis not (A1).

In another aspect of the invention, R⁶ is as defined above provided thatit is not an aliphatic, saturated or unsaturated group [in which thegroup contains three to thirteen carbon atoms and at least one siliconatom and, optionally, one to three heteroatoms, each independentlyselected from oxygen, nitrogen and sulphur, and the group is optionallysubstituted by up to four independently selected halogen atoms].

In a further aspect of the invention, A is as defined above providedthat it is not (A1) when R⁶ is an aliphatic, saturated or unsaturatedgroup [in which the group contains three to thirteen carbon atoms and atleast one silicon atom and, optionally, one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur, and the groupis optionally substituted by up to four independently selected halogenatoms].

Preferably Q is a single bond.

Preferably n is 0.

Preferably m is 0.

Preferably A is selected from formulae (A1), (A2), (A3), (A16), (A17),(A18), (A19), (A20) and (A22).

More preferably A is selected from formulae (A1); (A2), (A18), (A19) and(A22).

Even more preferably A is selected from one of the followingortho-substituted rings:

where R¹³ and R¹⁴ are each, independently, selected from H and C₁₋₄alkyl.

Preferably X is O, NR¹⁸ or (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

More preferably X is O or (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

Even more preferably X is (CR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n).

Most preferably X is (CR¹⁹R²⁰).

Preferably R¹ is C₁₋₄ alkyl, C₁₋₄ haloalkyl, NO₂, CN or OCF₃.

More preferably R¹ is CHF₂, CF₃, CH₂F, CF₂Cl, CH₃ or C₂H₅.

Even more preferably R¹ is CHF₂, CF₃, CH₂F, CF₂Cl or CH₃.

Most preferably R¹ is CHF₂, CF₃ or CH₂F.

Preferably R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy(C₁₋₄)alkyl orC₁₋₄ alkylthio(C₁₋₄)alkyl.

More preferably R² is CH₃, CF₃, C₂H₅, CH₂OCH₃ or CH₂SCH₃.

Even more preferably R² is CH₃ or C₂H₅.

Most preferably R² is CH₃.

Preferably R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ or COR⁵.

More preferably R³ is H, CH₂C≡CH, CH═C═CH₂, CH₂CH═CH₂ or COCH₃.

Still more preferably R³ is H, CH₂C≡CH, CH═C═CH₂ or CH₂CH═CH₂.

Even more preferably R³ is H, CH₂C≡CH or CH═C═CH₂.

Most preferably R³ is H.

Preferably each R⁴ is, independently, H, halogen, C₁₋₄ alkyl or C₁₋₄alkoxy.

More preferably each R⁴ is, independently, H, Cl, Br, CH₃ or CH₃O.

Still more preferably each R⁴ is, independently, H, Cl or CH₃.

Most preferably each R⁴ is H.

Preferably R⁵ is H, C₁₋₆ alkyl, C₁₋₄ alkoxy or C₁₋₄ alkoxy(C₁₋₄)alkyl.

More preferably R⁵ is H, methyl, OC(CH₃)₃ or CH₂OCH₃.

Even more preferably R⁵ is H or methyl.

Preferably R⁶ is chosen from C₃₋₁₀ alkyl, C₃₋₉ haloalkyl, C₃₋₇cycloalkyl [optionally substituted by C₃ cycloalkyl (itself optionallysubstituted by C₁₋₂ alkyl) or by up to two C₁₋₄ alkyl groups], analiphatic group [which contains three to ten carbon atoms and at leastone silicon atom and, optionally, one oxygen atom], thienyl [optionallysubstituted by halo], furyl [optionally substituted by halo], pyridyl[optionally substituted by halo], oxazolyl, isoxazolyl and

where R^(c) and R^(d) are, independently, H, Cl, Br, F, I, CN, NO₂, C₁₋₄alkyl, CF₃, SCF₃, OCF₃, CH═NOH, CH═N—OC₁₋₆ alkyl, C≡CH, C≡C—Si(CH₃)₃,C(H)═CH₂ or C(H)═CH(C₁₋₄ alkyl).

More preferably R⁶ is C₃₋₇ alkyl, C₃₋₆ cycloalkyl [optionallysubstituted by C₁₋₄ alkyl or a C₃ cycloalkyl (itself optionallysubstituted by C₁₋₂ alkyl)], an aliphatic group (which contains three toeight carbon atoms and at least one silicon atom) or

where R^(e) is Cl, Br, F, CF₃, OCF₃, CH═N—OC₁₋₄ alkyl, C≡CH,C≡C—Si(CH₃)₃ or C(H)═CH₂ [in one aspect it is preferred that R^(e) isCl, Br, F, CF₃, OCF₃, CH═N—OC₁₋₄ alkyl, C≡CH or C(H)═CH₂].

Even more preferably R⁶ is chosen from one of the following moieties:

where R^(e) is Cl, Br, F, CF₃, C≡CH, C≡C—Si(CH₃)₃ or CH═N—OC₁₋₄ alkyl[in one aspect it is preferred that R^(e) is Cl, Br, F, CF₃, C≡CH orCH═N—OC₁₋₄ alkyl].

Preferably R⁷ is H, F or CH₃.

Preferably R⁸ is H.

Preferably R⁹ is H.

Preferably R¹⁰ is H.

Preferably R¹¹ is H.

Preferably R¹² is H.

Preferably R¹³, R¹⁴, R¹⁵, R¹⁶ are each, independently, H, CH₃, C₂H₅,CF₃, CH₃O, C(O)CH₃ or CH₃OCH₂.

More preferably R¹³, R¹⁴, R¹⁵, R¹⁶ are each, independently, H or CH₃.

Preferably R¹⁷ is H.

Preferably R¹⁸ is H, CH₃, C₂H₅, C(O)OC₁₋₄ alkyl (optionally substitutedwith halogen or C₁₋₄ alkoxy) or COH.

More preferably R¹⁸ is C(O)OC₁₋₄ alkyl (optionally substituted withhalogen or C₁₋₄ alkoxy) or COH.

Even more preferably R¹⁸ is C(O)OC₁₋₄ alkyl (optionally substituted withhalogen or C₁₋₄ alkoxy).

Most preferably R¹⁸ is C(O)OC₁₋₄ alkyl.

Preferably R¹⁹ and R²⁰ are each, independently, H, halogen, C₁₋₅ alkyl,C₁₋₃ alkoxy, CH₂O, C₃₋₆ cycloalkyl, CH₂O—C(═O)CH₃, CH₂—C₃₋₆ cycloalkylor benzyl; or R¹⁹ and R²⁰ together with the carbon atom to which theyare attached form a carbonyl group, a 3-5 membered carbocyclic ring,C₁₋₅ alkylidene or C₃₋₆ cycloalkylidene.

More preferably R¹⁹ and R²⁰ are, independently, H, CH₃, C₂H₅, n-C₃H₇,i-C₃H₇, i-C₄H₉, CH(C₂H₅)₂, CH₂-cyclopropyl or cyclopentyl; or R¹⁹ andR²⁰ together with the carbon atom to which they are attached form a3-membered carbocyclic ring.

Preferably R²¹ is H or CH₃.

Preferably R²² is H or CH₃.

Preferably R²³ is H or CH₃.

Preferably R²⁴ is H or CH₃.

Compounds of formula (II):

where R¹ and R² are as defined above for a compound of formula (I) and Yis halogen, hydroxy or C₁₋₅ alkoxy, are useful as intermediates in thepreparation of compounds of formula (I).

Some compounds of formula (II) are already known in the literature [B.Iddon et al. J. Chem. Soc. Perkin Trans. 1, 1341 (1996); M. Begtrup etal., Acta Chemica Scald., 19, 2022 (1965); D. R. Buckle et al., J. Chem.Res, Syn. 10, 292 (1982); and A. Peratoner et al., Sci. Fis. Mat. Nat.Rend 5, 16 (1907)] but others are novel.

Therefore, in another aspect the present invention provides a compoundof formula (II) where R¹ and R² are as defined above for a compound offormula (I) and Y is halogen, hydroxy or C₁₋₅ alkoxy; provided that whenR¹ is chloro and R² is 4-CH₃O—C₆H₄—CH₂—, Y is not C₂H₅O; when R¹ is CH₃Oand R² is CH₃, Y is not C₂H₅O; when R¹ is bromo and R² is CH₃OCH₂, Y isnot CH₃O; and when R¹ is CH₃ and R² is C₂H₅, Y is not OH.

Preferably Y is hydroxy, chloro, fluoro or C₁₋₃ alkoxy.

Some compounds of formula (IIIa) are also novel but some are describedin the literature [see, for example, L. A Paquette et al., J. Amer. ChemSoc. 99, 3734 (1977); H. Plieninger et al., Chem. Ber. 109, 2121 (1976);Kasansski et al., Zh. Obshch. Khim. (1959), 29, 2588; and A. J. Kirby etal., J. Chem. Soc., Perkin Trans. 2, 1997, 1081].

Anilines of formula (IIIa) are novel when R¹³, R¹⁴, R¹⁵, R¹⁶, Q and Xare as defined above for a compound of formula (I); provided that whenR¹³, R¹⁴, R¹⁵ and R¹⁶ are each H then X is not CH₂ when Q is a doublebond and X is not CH₂CH₂ when Q is a single bond or a double bond; andwhen R¹³ is CH₃, R¹⁴ is OCH₃ and R¹⁵ and R¹⁶ are both H then X is notCH₂CH₂ when Q is a single bond.

Therefore, in a further aspect, the present invention provides acompound of formula (IIIa) where R¹³, R¹⁴, R¹⁵, R¹⁶, Q and X are asdefined above for a compound of formula (I); provided that when R¹³,R¹⁴, R¹⁵ and R¹⁶ are each H then X is not CH₂ when Q is a double bondand X is not CH₂CH₂ when Q is a single bond or a double bond; and whenR¹³ is CH₃, R¹⁴ is OCH₃ and R¹⁵ and R¹⁶ are both H then X is not CH₂CH₂when Q is a single bond.

The compounds of formula (I), (II) and (IIIa) may exist as differentgeometric or optical isomers or in different tautomeric forms. Thisinvention covers, for each formula, all such isomers and tautomers andmixtures thereof in all proportions as well as isotopic forms such asdeuterated compounds.

The compounds in Tables 1 to 28 below illustrate compounds of theinvention.

Table 1 provides 59 compounds of formula (II) wherein R¹, R² and Y areas defined in Table 1.

TABLE 1 Compound Number R¹ R² Y 1.01 CHF₂ CH₃ OH 1.02 CHF₂ CH₃ Cl 1.03CHF₂ CH₃ OCH₃ 1.04 CHF₂ CH₃ OC₂H₅ 1.05 CHF₂ CH₃ OC₃H₇(n) 1.06 CHF₂ CH₃OC₃H₇(i) 1.07 CHF₂ C₂H₅ OH 1.08 CHF₂ C₂H₅ Cl 1.09 CHF₂ C₂H₅ OCH₃ 1.10CHF₂ C₂H₅ OC₂H₅ 1.11 CHF₂ C₂H₅ OC₃H₇(n) 1.12 CHF₂ C₂H₅ OC₃H₇(i) 1.13 CF₃CH₃ OH 1.14 CF₃ CH₃ Cl 1.15 CF₃ CH₃ OCH₃ 1.16 CF₃ CH₃ OC₂H₅ 1.17 CF₃ CH₃OC₃H₇(n) 1.18 CF₃ CH₃ OC₃H₇(i) 1.19 CF₃ C₂H₅ OH 1.20 CF₃ C₂H₅ Cl 1.21CF₃ C₂H₅ OCH₃ 1.22 CF₃ C₂H₅ OC₂H₅ 1.23 CF₃ C₂H₅ OC₃H₇(n) 1.24 CF₃ C₂H₅OC₃H₇(i) 1.25 CF₃ CH₂OCH₃ OH 1.26 CF₃ CH₂OCH₃ Cl 1.27 CF₃ CH₂OCH₃ OCH₃1.28 CF₃ CH₂OCH₃ OC₂H₅ 1.29 CF₃ CH₂OCH₃ OC₃H₇(n) 1.30 CF₃ CH₂OCH₃OC₃H₇(i) 1.31 CF₃ CH₃ F 1.32 CHF₂ CH₃ F 1.33 CHF₂ CH₂OCH₃ OH 1.34 CHF₂CH₂OCH₃ OCH₃ 1.35 CHF₂ CH₂OCH₃ OC₂H₅ 1.36 CF₃ CH₂SCH₃ OH 1.37 CF₃CH₂SCH₃ OCH₃ 1.38 CN CH₃ OCH₃ 1.39 OCF₃ CH₃ OCH₃ 1.40 NO₂ CH₃ OCH₃ 1.41CH₃ CH₃ OH 1.42 CH₃ CH₃ OCH₃ 1.43 CH₃ CH₃ Cl 1.44 CH₃ C₂H₅ OH 1.45 C₂F₅CH₃ OCH₃ 1.46 CF₃ CF₃ OCH₃ 1.47 CH₃ CF₃ OCH₃ 1.48 CH₂F CH₃ OH 1.49 CH₂FCH₃ Cl 1.50 CH₂F CH₃ OCH₃ 1.51 CH₂F CH₃ OC₂H₅ 1.52 CH₂F CH₃ OC₃H₇(n)1.53 CH₂F CH₃ OC₃H₇(i) 1.54 CH₂F C₂H₅ OH 1.55 CH₂F C₂H₅ Cl 1.56 CH₂FC₂H₅ OCH₃ 1.57 CH₂F C₂H₅ OC₂H₅ 1.58 CH₂F C₂H₅ OC₃H₇(n) 1.59 CH₂F C₂H₅OC₃H₇(i)

Table X represents Table 2 [when X is 2], Table 3 [when X is 3], Table 4[when X is 4], Table 5 [when X is 5], Table 6 [when X is 6] andrepresents Table 7 [when X is 7].

TABLE X Cmpd. No. R² R³ R⁶ R⁷ X.001 CH₃ H phenyl H X.002 CH₃ CH₂C≡CHphenyl H X.003 CH₃ H 2′-fluorophenyl H X.004 CH₃ H 3′-fluorophenyl HX.005 CH₃ H 4′-fluorophenyl H X.006 C₂H₅ H 4′-fluorophenyl H X.007CH₂OCH₃ H 4′-fluorophenyl H X.008 CH₃ COCH₃ 4′-fluorophenyl H X.009 CH₃COCH₂OCH₃ 4′-fluorophenyl H X.010 CH₃ CH₂C≡CH 4′-fluorophenyl H X.011CH₃ CH═C═CH₂ 4′-fluorophenyl H X.012 CH₃ COO-tert-Bu 4′-fluorophenyl HX.013 CH₃ H 4′-fluorophenyl F X.014 CH₃ H 4′-fluorophenyl CH₃ X.015 CH₃H 2′-chlorophenyl H X.016 CH₃ H 3′-chlorophenyl H X.017 CH₃ H4′-chlorophenyl H X.018 C₂H₅ H 4′-chlorophenyl H X.019 CH₂OCH₃ H4′-chlorophenyl H X.020 CH₃ COCH₃ 4′-chlorophenyl H X.021 CH₃ COCH₂OCH₃4′-chlorophenyl H X.022 CH₃ CH₂C≡CH 4′-chlorophenyl H X.023 CH₃ CH═C═CH₂4′-chlorophenyl H X.024 CH₃ COO-tert-Bu 4′-chlorophenyl H X.025 CH₃ H4′-chlorophenyl F X.026 CH₃ H 4′-chlorophenyl CH₃ X.027 CH₃ H2′-bromophenyl H X.028 CH₃ H 3′-bromophenyl H X.029 CH₃ H 4′-bromophenylH X.030 C₂H₅ H 4′-bromophenyl H X.031 CH₂OCH₃ H 4′-bromophenyl H X.032CH₃ COCH₃ 4′-bromophenyl H X.033 CH₃ COCH₂OCH₃ 4′-bromophenyl H X.034CH₃ CH₂C≡CH 4′-bromophenyl H X.035 CH₃ CH═C═CH₂ 4′-bromophenyl H X.036CH₃ COO-tert-Bu 4′-bromophenyl H X.037 CH₃ H 4′-bromophenyl F X.038 CH₃H 4′-bromophenyl CH₃ X.039 CH₃ H 2′-iodophenyl H X.040 CH₃ H3′-iodophenyl H X.041 CH₃ H 4′-iodophenyl H X.042 CH₃ H 2′-CF₃-phenyl HX.043 CH₃ H 3′-CF₃-phenyl H X.044 CH₃ H 4′-CF₃-phenyl H X.045 C₂H₅ H4′-CF₃-phenyl H X.046 CH₂OCH₃ H 4′-CF₃-phenyl H X.047 CH₃ COCH₃4′-CF₃-phenyl H X.048 CH₃ COCH₂OCH₃ 4′-CF₃-phenyl H X.049 CH₃ CH₂C≡CH4′-CF₃-phenyl H X.050 CH₃ COO-tert-Bu 4′-CF₃-phenyl H X.051 CH₃ H2′-OCF₃-phenyl H X.052 CH₃ H 3′-OCF₃-phenyl H X.053 CH₃ H 4′-OCF₃-phenylH X.054 C₂H₅ H 4′-OCF₃-phenyl H X.055 CH₂OCH₃ H 4′-OCF₃-phenyl H X.056CH₃ COCH₃ 4′-OCF₃-phenyl H X.057 CH₃ COCH₂OCH₃ 4′-OCF₃-phenyl H X.058CH₃ CH₂C≡CH 4′-OCF₃-phenyl H X.059 CH₃ COO-tert-Bu 4′-OCF₃-phenyl HX.060 CH₃ CH═C═CH₂ 4′-OCF₃-phenyl H X.061 CH₃ H 4′-SCF₃-phenyl H X.062CH₃ H 2′-CH═NOH-phenyl H X.063 CH₃ H 3′-CH═NOH-phenyl H X.064 CH₃ H4′-CH═NOH-phenyl H X.065 CH₃ H 2′-CH═NOCH₃-phenyl H X.066 CH₃ H3′-CH═NOCH₃-phenyl H X.067 CH₃ H 4′-CH═NOCH₃-phenyl H X.068 CH₃ H2′-CH═NOC₂H₅-phenyl H X.069 CH₃ H 3′-CH═NOC₂H₅-phenyl H X.070 CH₃ H4′-CH═NOC₂H₅-phenyl H X.071 CH₃ H 2′-CN-phenyl H X.072 CH₃ H3′-CN-phenyl H X.073 CH₃ H 4′-CN-phenyl H X.074 CH₃ H 2′-NO₂-phenyl HX.075 CH₃ H 3′-NO₂-phenyl H X.076 CH₃ H 4′-NO₂-phenyl H X.077 CH₃ H3′,4′-difluorophenyl H X.078 C₂H₅ H 3′,4′-difluorophenyl H X.079 CH₂OCH₃H 3′,4′-difluorophenyl H X.080 CH₃ COCH₃ 3′,4′-difluorophenyl H X.081CH₃ COCH₂OCH₃ 3′,4′-difluorophenyl H X.082 CH₃ CH₂C≡CH3′,4′-difluorophenyl H X.083 CH₃ COO-tert-Bu 3′,4′-difluorophenyl HX.084 CH₃ CH═C═CH₂ 3′,4′-difluorophenyl H X.085 CH₃ H3′,4′-difluorophenyl F X.086 CH₃ H 3′,4′-difluorophenyl CH₃ X.087 CH₃ H3′,4′-dichlorophenyl H X.088 C₂H₅ H 3′,4′-dichlorophenyl H X.089 CH₂OCH₃H 3′,4′-dichlorophenyl H X.090 CH₃ COCH₃ 3′,4′-dichlorophenyl H X.091CH₃ COCH₂OCH₃ 3′,4′-dichlorophenyl H X.092 CH₃ CH₂C≡CH3′,4′-dichlorophenyl H X.093 CH₃ COO-tert-Bu 3′,4′-dichlorophenyl HX.094 CH₃ CH═C═CH₂ 3′,4′-dichlorophenyl H X.095 CH₃ H3′,4′-dichlorophenyl F X.096 CH₃ H 3′,4′-dichlorophenyl CH₃ X.097 CH₃ H4′-chloro-3′-fluoro-phenyl H X.098 C₂H₅ H 4′-chloro-3′-fluoro-phenyl HX.099 CH₂OCH₃ H 4′-chloro-3′-fluoro-phenyl H X.100 CH₃ COCH₃4′-chloro-3′-fluoro-phenyl H X.101 CH₃ COCH₂OCH₃4′-chloro-3′-fluoro-phenyl H X.102 CH₃ CH₂C≡CH4′-chloro-3′-fluoro-phenyl H X.103 CH₃ COO-tert-Bu4′-chloro-3′-fluoro-phenyl H X.104 CH₃ CH═C═CH₂4′-chloro-3′-fluoro-phenyl H X.105 CH₃ H 4′-chloro-3′-fluoro-phenyl FX.106 CH₃ H 4′-chloro-3′-fluoro-phenyl CH₃ X.107 CH₃ H3′-chloro-4′-fluoro-phenyl H X.108 C₂H₅ H 3′-chloro-4′-fluoro-phenyl HX.109 CH₂OCH₃ H 3′-chloro-4′-fluoro-phenyl H X.110 CH₃ COCH₃3′-chloro-4′-fluoro-phenyl H X.111 CH₃ COCH₂OCH₃3′-chloro-4′-fluoro-phenyl H X.112 CH₃ CH₂C≡CH3′-chloro-4′-fluoro-phenyl H X.113 CH₃ COO-tert-Bu3′-chloro-4′-fluoro-phenyl H X.114 CH₃ CH═C═CH₂3′-chloro-4′-fluoro-phenyl H X.115 CH₃ H 3′-chloro-4′-fluoro-phenyl FX.116 CH₃ H 3′-chloro-4′-fluoro-phenyl CH₃ X.117 CH₃ H2′-4′-dichloro-phenyl H X.118 CH₂OCH₃ H 2′-4′-dichloro-phenyl H X.119CH₃ H 2′-4′-difluoro-phenyl H X.120 CH₂OCH₃ H 2′-4′-difluoro-phenyl HX.121 CH₃ H CH₂CH₂CH₃ H X.122 C₂H₅ H CH₂CH₂CH₃ H X.123 CH₂OCH₃ HCH₂CH₂CH₃ H X.124 CH₃ CH₂C≡CH CH₂CH₂CH₃ H X.125 CH₃ H CH₂CH₂CH₂CH₃ HX.126 C₂H₅ H CH₂CH₂CH₂CH₃ H X.127 CH₂OCH₃ H CH₂CH₂CH₂CH₃ H X.128 CH₃CH₂C≡CH CH₂CH₂CH₂CH₃ H X.129 CH₃ H CH₂CH₂CH₂CH₃ F X.130 CH₃ HCH₂CH₂CH₂CH₃ CH₃ X.131 CH₃ H CH₂CH₂CH₂(C₂H₅) H X.132 C₂H₅ HCH₂CH₂CH₂(C₂H₅) H X.133 CH₂OCH₃ H CH₂CH₂CH₂(C₂H₅) H X.134 CH₃ CH₂C≡CHCH₂CH₂CH₂(C₂H₅) H X.135 CH₃ H CH₂CH₂CH₂(C₂H₅) F X.136 CH₃ HCH₂CH₂CH₂(C₂H₅) CH₃ X.137 CH₃ H CH₂CH₂CH(CH₃)₂ H X.138 C₂H₅ HCH₂CH₂CH(CH₃)₂ H X.139 CH₂OCH₃ H CH₂CH₂CH(CH₃)₂ H X.140 CH₃ COCH₃CH₂CH₂CH(CH₃)₂ H X.141 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)₂ H X.142 CH₃ CH₂C≡CHCH₂CH₂CH(CH₃)₂ H X.143 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)₂ H X.144 CH₃CH═C═CH₂ CH₂CH₂CH(CH₃)₂ H X.145 CH₃ H CH₂CH₂CH(CH₃)₂ F X.146 CH₃ HCH₂CH₂CH(CH₃)₂ CH₃ X.147 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) H X.148 C₂H₅ HCH₂CH₂CH(CH₃)(C₂H₅) H X.149 CH₂OCH₃ H CH₂CH₂CH(CH₃)(C₂H₅) H X.150 CH₃COCH₃ CH₂CH₂CH(CH₃)(C₂H₅) H X.151 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)(C₂H₅) HX.152 CH₃ CH₂C≡CH CH₂CH₂CH(CH₃)(C₂H₅) H X.153 CH₃ COO-tert-BuCH₂CH₂CH(CH₃)(C₂H₅) H X.154 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)(C₂H₅) H X.155 CH₃H CH₂CH₂CH(CH₃)(C₂H₅) F X.156 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) CH₃ X.157 CH₃ HCH₂CH₂CH(C₂H₅)₂ H X.158 C₂H₅ H CH₂CH₂CH(C₂H₅)₂ H X.159 CH₂OCH₃ HCH₂CH₂CH(C₂H₅)₂ H X.160 CH₃ COCH₃ CH₂CH₂CH(C₂H₅)₂ H X.161 CH₃ COCH₂OCH₃CH₂CH₂CH(C₂H₅)₂ H X.162 CH₃ CH₂C≡CH CH₂CH₂CH(C₂H₅)₂ H X.163 CH₃COO-tert-Bu CH₂CH₂CH(C₂H₅)₂ H X.164 CH₃ CH═C═CH₂ CH₂CH₂CH(C₂H₅)₂ H X.165CH₃ H CH₂CH₂CH(C₂H₅)₂ F X.166 CH₃ H CH₂CH₂CH(C₂H₅)₂ CH₃ X.167 CH₃ HCH₂CH₂C(CH₃)₃ H X.168 C₂H₅ H CH₂CH₂C(CH₃)₃ H X.169 CH₂OCH₃ HCH₂CH₂C(CH₃)₃ H X.170 CH₃ COCH₃ CH₂CH₂C(CH₃)₃ H X.171 CH₃ COCH₂OCH₃CH₂CH₂C(CH₃)₃ H X.172 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₃ H X.173 CH₃ COO-tert-BuCH₂CH₂C(CH₃)₃ H X.174 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₃ H X.175 CH₃ HCH₂CH₂C(CH₃)₃ F X.176 CH₃ H CH₂CH₂C(CH₃)₃ CH₃ X.177 CH₃ HCH₂CH₂C(CH₃)₂(C₂H₅) H X.178 C₂H₅ H CH₂CH₂C(CH₃)₂(C₂H₅) H X.179 CH₂OCH₃ HCH₂CH₂C(CH₃)₂(C₂H₅) H X.180 CH₃ COCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) H X.181 CH₃COCH₂OCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) H X.182 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₂(C₂H₅) HX.183 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₂(C₂H₅) H X.184 CH₃ CH═C═CH₂CH₂CH₂C(CH₃)₂(C₂H₅) H X.185 CH₃ H CH₂CH₂C(CH₃)₂(C₂H₅) F X.186 CH₃ HCH₂CH₂C(CH₃)₂(C₂H₅) CH₃ X.187 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ H X.188 C₂H₅ HCH₂CH₂C(CH₃)(C₂H₅)₂ H X.189 CH₂OCH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ H X.190 CH₃COCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ H X.191 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ HX.192 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)(C₂H₅)₂ H X.193 CH₃ COO-tert-BuCH₂CH₂C(CH₃)(C₂H₅)₂ H X.194 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)(C₂H₅)₂ H X.195 CH₃H CH₂CH₂C(CH₃)(C₂H₅)₂ F X.196 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ CH₃ X.197 CH₃ HCH(CH₃)CH₂CH₃ H X.198 C₂H₅ H CH(CH₃)CH₂CH₃ H X.199 CH₂OCH₃ HCH(CH₃)CH₂CH₃ H X.200 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₃ H X.201 CH₃ HCH(C₂H₅)CH₂CH₃ H X.202 C₂H₅ H CH(C₂H₅)CH₂CH₃ H X.203 CH₂OCH₃ HCH(C₂H₅)CH₂CH₃ H X.204 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₃ H X.205 CH₃ HCH(CF₃)CH₂CH₃ H X.206 C₂H₅ H CH(CF₃)CH₂CH₃ H X.207 CH₂OCH₃ HCH(CF₃)CH₂CH₃ H X.208 CH₃ CH₂C≡CH CH(CF₃)CH₂CH₃ H X.209 CH₃ HCH(CH₃)CH₂CH₂CH₃ H X.210 C₂H₅ H CH(CH₃)CH₂CH₂CH₃ H X.211 CH₂OCH₃ HCH(CH₃)CH₂CH₂CH₃ H X.212 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₂CH₃ H X.213 CH₃ HCH(C₂H₅)CH₂CH₂CH₃ H X.214 C₂H₅ H CH(C₂H₅)CH₂CH₂CH₃ H X.215 CH₂OCH₃ HCH(C₂H₅)CH₂CH₂CH₃ H X.216 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₂CH₃ H X.217 CH₃ HCH(CF₃)CH₂CH₂CH₃ H X.218 C₂H₅ H CH(CF₃)CH₂CH₂CH₃ H X.219 CH₃ HCH(CH₃)CH₂CH(CH₃)₂ H X.220 C₂H₅ H CH(CH₃)CH₂CH(CH₃)₂ H X.221 CH₂OCH₃ HCH(CH₃)CH₂CH(CH₃)₂ H X.222 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)₂ H X.223 CH₃COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)₂ H X.224 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)₂ HX.225 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)₂ H X.226 CH₃ CH═C═CH₂CH(CH₃)CH₂CH(CH₃)₂ H X.227 CH₃ H CH(CH₃)CH₂CH(CH₃)₂ F X.228 CH₃ HCH(CH₃)CH₂CH(CH₃)₂ CH₃ X.229 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.230 C₂H₅H CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.231 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) HX.232 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.233 CH₃ COCH₂OCH₃CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.234 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)(C₂H₅) HX.235 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.236 CH₃ CH═C═CH₂CH(CH₃)CH₂CH(CH₃)(C₂H₅) H X.237 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) F X.238CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) CH₃ X.239 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ HX.240 C₂H₅ H CH(CH₃)CH₂CH(C₂H₅)₂ H X.241 CH₂OCH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ HX.242 CH₃ COCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ H X.243 CH₃ COCH₂OCH₃CH(CH₃)CH₂CH(C₂H₅)₂ H X.244 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(C₂H₅)₂ H X.245 CH₃COO-tert-Bu CH(CH₃)CH₂CH(C₂H₅)₂ H X.246 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(C₂H₅)₂H X.247 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ F X.248 CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ CH₃X.249 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ H X.250 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)₂ HX.251 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ H X.252 CH₃ COCH₃CH(C₂H₅)CH₂CH(CH₃)₂ H X.253 CH₃ COCH₂OCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ H X.254CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)₂ H X.255 CH₃ COO-tert-BuCH(C₂H₅)CH₂CH(CH₃)₂ H X.256 CH₃ CH═C═CH₂ CH(C₂H₅)CH₂CH(CH₃)₂ H X.257 CH₃H CH(C₂H₅)CH₂CH(CH₃)₂ F X.258 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ CH₃ X.259 CH₃ HCH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.260 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.261CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.262 CH₃ CH₂C≡CHCH(C₂H₅)CH₂CH(CH₃)(C₂H₅) H X.263 CH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.264 C₂H₅H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.265 CH₂OCH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.266CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH(C₂H₅)₂ H X.267 CH₃ H CH(CF₃)CH₂CH(CH₃)₂ HX.268 C₂H₅ H CH(CF₃)CH₂CH(CH₃)₂ H X.269 CH₂OCH₃ H CH(CF₃)CH₂CH(CH₃)₂ HX.270 CH₃ CH₂C≡CH CH(CF₃)CH₂CH(CH₃)₂ H X.271 CH₃ HCH(CF₃)CH₂CH(CH₃)(C₂H₅) H X.272 CH₃ H CH(CF₃)CH₂CH(C₂H₅)₂ H X.273 CH₃ HCH(CH₃)CH₂C(CH₃)₃ H X.274 C₂H₅ H CH(CH₃)CH₂C(CH₃)₃ H X.275 CH₂OCH₃ HCH(CH₃)CH₂C(CH₃)₃ H X.276 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₃ H X.277 CH₃COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₃ H X.278 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₃ HX.279 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₃ H X.280 CH₃ CH═C═CH₂CH(CH₃)CH₂C(CH₃)₃ H X.281 CH₃ H CH(CH₃)CH₂C(CH₃)₃ F X.282 CH₃ HCH(CH₃)CH₂C(CH₃)₃ CH₃ X.283 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.284 C₂H₅ HCH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.285 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) HX.286 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.287 CH₃ COCH₂OCH₃CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.288 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₂(C₂H₅) HX.289 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.290 CH₃ CH═C═CH₂CH(CH₃)CH₂C(CH₃)₂(C₂H₅) H X.291 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) F X.292CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) CH₃ X.293 CH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ HX.294 C₂H₅ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.295 CH₂OCH₃ HCH(CH₃)CH₂C(CH₃)(C₂H₅)₂ H X.296 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ HX.297 CH₃ H CH(C₂H₅)CH₂C(CH₃)₃ H X.298 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₃ H X.299CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₃ H X.300 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₃ HX.301 CH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.302 C₂H₅ HCH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.303 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) HX.304 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) H X.305 CH₃ HCH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.306 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.307CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.308 CH₃ CH₂C≡CHCH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ H X.309 CH₃ H CH(CF₃)CH₂C(CH₃)₃ H X.310 C₂H₅ HCH(CF₃)CH₂C(CH₃)₃ H X.311 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₃ H X.312 CH₃CH₂C≡CH CH(CF₃)CH₂C(CH₃)₃ H X.313 CH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.314C₂H₅ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.315 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅)H X.316 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₂(C₂H₅) H X.317 CH₃ HCH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.318 C₂H₅ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.319CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.320 CH₃ CH₂C≡CHCH(CF₃)CH₂C(CH₃)(C₂H₅)₂ H X.321 CH₃ H 2′-tert-butyl-cyclopropyl H X.322C₂H₅ H 2′-tert-butyl-cyclopropyl H X.323 CH₂OCH₃ H2′-tert-butyl-cyclopropyl H X.324 CH₃ CH₂C≡CH 2′-tert-butyl-cyclopropylH X.325 CH₃ H 2′-isobutyl-cyclopropyl H X.326 C₂H₅ H2′-isobutyl-cyclopropyl H X.327 CH₂OCH₃ H 2′-isobutyl-cyclopropyl HX.328 CH₃ CH₂C≡CH 2′-isobutyl-cyclopropyl H X.329 CH₃ H4′,4′-dimethyl-cyclobutyl H X.330 C₂H₅ H 4′,4′-dimethyl-cyclobutyl HX.331 CH₂OCH₃ H 4′,4′-dimethyl-cyclobutyl H X.332 CH₃ CH₂C≡CH4′,4′-dimethyl-cyclobutyl H X.333 CH₃ H cyclopentyl H X.334 C₂H₅ Hcyclopentyl H X.335 CH₂OCH₃ H cyclopentyl H X.336 CH₃ CH₂C≡CHcyclopentyl H X.337 CH₃ H 3′-methyl-cyclopentyl H X.338 C₂H₅ H3′-methyl-cyclopentyl H X.339 CH₂OCH₃ H 3′-methyl-cyclopentyl H X.340CH₃ CH₂C≡CH 3′-methyl-cyclopentyl H X.341 CH₃ H cyclohexyl H X.342 C₂H₅H cyclohexyl H X.343 CH₂OCH₃ H cyclohexyl H X.344 CH₃ CH₂C≡CH cyclohexylH X.345 CH₃ H 3′-methyl-cyclohexyl H X.346 C₂H₅ H 3′-methyl-cyclohexyl HX.347 CH₂OCH₃ H 3′-methyl-cyclohexyl H X.348 CH₃ CH₂C≡CH3′-methyl-cyclohexyl H X.349 CH₃ H 4′-methyl-cyclohexyl H X.350 C₂H₅ H4′-methyl-cyclohexyl H X.351 CH₂OCH₃ H 4′-methyl-cyclohexyl H X.352 CH₃CH₂C≡CH 4′-methyl-cyclohexyl H X.353 CH₃ H cycloheptyl H X.354 C₂H₅ Hcycloheptyl H X.355 CH₂OCH₃ H cycloheptyl H X.356 CH₃ CH₂C≡CHcycloheptyl H X.357 CH₃ H 2′-thienyl H X.358 C₂H₅ H 2′-thienyl H X.359CH₂OCH₃ H 2′-thienyl H X.360 CH₃ CH₂C≡CH 2′-thienyl H X.361 CH₃ H3′-thienyl H X.362 C₂H₅ H 3′-thienyl H X.363 CH₂OCH₃ H 3′-thienyl HX.364 CH₃ CH₂C≡CH 3′-thienyl H X.365 CH₃ H 5′-chloro-2′-thienyl H X.366C₂H₅ H 5′-chloro-2′-thienyl H X.367 CH₂OCH₃ H 5′-chloro-2′-thienyl HX.368 CH₃ CH₂C≡CH 5′-chloro-2′-thienyl H X.369 CH₃ H 2′-furyl H X.370C₂H₅ H 2′-furyl H X.371 CH₂OCH₃ H 2′-furyl H X.372 CH₃ CH₂C≡CH 2′-furylH X.373 CH₃ H 5′-chloro-2′-furyl H X.374 C₂H₅ H 5′-chloro-2′-furyl HX.375 CH₂OCH₃ H 5′-chloro-2′-furyl H X.376 CH₃ CH₂C≡CH5′-chloro-2′-furyl H X.377 CH₃ H 2′-pyridyl H X.378 C₂H₅ H 2′-pyridyl HX.379 CH₂OCH₃ H 2′-pyridyl H X.380 CH₃ CH₂C≡CH 2′-pyridyl H X.381 CH₃ H3′-pyridyl H X.382 C₂H₅ H 3′-pyridyl H X.383 CH₂OCH₃ H 3′-pyridyl HX.384 CH₃ CH₂C≡CH 3′-pyridyl H X.385 CH₃ H 4′-pyridyl H X.386 C₂H₅ H4′-pyridyl H X.387 CH₂OCH₃ H 4′-pyridyl H X.388 CH₃ CH₂C≡CH 4′-pyridyl HX.389 CH₃ H 6′-chloro-3′-pyridyl H X.390 C₂H₅ H 6′-chloro-3′-pyridyl HX.391 CH₂OCH₃ H 6′-chloro-3′-pyridyl H X.392 CH₃ CH₂C≡CH6′-chloro-3′-pyridyl H X.393 CH₃ H 6′-fluoro-3′-pyridyl H X.394 C₂H₅ H6′-fluoro-3′-pyridyl H X.395 CH₂OCH₃ H 6′-fluoro-3′-pyridyl H X.396 CH₃CH₂C≡CH 6′-fluoro-3′-pyridyl H X.397 CH₃ H 6′-bromo-3′-pyridyl H X.398C₂H₅ H 6′-bromo-3′-pyridyl H X.399 CH₂OCH₃ H 6′-bromo-3′-pyridyl H X.400CH₃ CH₂C≡CH 6′-bromo-3′-pyridyl H X.401 CH₃ H 2′-oxazolyl H X.402 CH₃ H3′-isoxazolyl H X.403 CH₃ H CH(CH₃)₂ H X.404 C₂H₅ H CH(CH₃)₂ H X.405CH₂OCH₃ H CH(CH₃)₂ H X.406 CH₃ CH₂C≡CH CH(CH₃)₂ H X.407 CH₃ H4′-CH═NO(n)-C₄H₉-phenyl H X.408 CH₃ H 4′-CH═NO(iso)-C₄H₉-phenyl H X.409CH₃ H 4′-CH═NO(iso)-C₃H₇-phenyl H X.410 CH₃ H 4′-CH═NO(n)-C₃H₇-phenyl HX.411 CH₃ H Si(CH₃)₃ H X.412 C₂H₅ H Si(CH₃)₃ H X.413 CH₂OCH₃ H Si(CH₃)₃H X.414 CH3 CH₂C≡CH Si(CH₃)₃ H X.415 CH₃ H CH₂Si(CH₃)₃ H X.416 C₂H₅ HCH₂Si(CH₃)₃ H X.416 CH₂OCH₃ H CH₂Si(CH₃)₃ H X.418 CH3 CH₂C≡CHCH₂Si(CH₃)₃ H X.419 CH₃ H CH(CH₃)Si(CH₃)₃ H X.420 C₂H₅ H CH(CH₃)Si(CH₃)₃H X.421 CH₂OCH₃ H CH(CH₃)Si(CH₃)₃ H X.422 CH3 CH₂C≡CH CH(CH₃)Si(CH₃)₃ HX.423 CH₃ H CH₂CH₂Si(CH₃)₃ H X.424 C₂H₅ H CH₂CH₂Si(CH₃)₃ H X.425 CH₂OCH₃H CH₂CH₂Si(CH₃)₃ H X.426 CH3 CH₂C≡CH CH₂CH₂Si(CH₃)₃ H X.427 CH₃ HCH(CH₃)CH₂Si(CH₃)₃ H X.428 C₂H₅ H CH(CH₃)CH₂Si(CH₃)₃ H X.429 CH₂OCH₃ HCH(CH₃)CH₂Si(CH₃)₃ H X.430 CH3 CH₂C≡CH CH(CH₃)CH₂Si(CH₃)₃ H X.431 CH₃ HCH₂CH₂CH₂Si(CH₃)₃ H X.432 C₂H₅ H CH₂CH₂CH₂Si(CH₃)₃ H X.433 CH₂OCH₃ HCH₂CH₂CH₂Si(CH₃)₃ H X.434 CH3 CH₂C≡CH CH₂CH₂CH₂Si(CH₃)₃ H X.435 CH₃ HCH₂Si(CH₃)₂C₂H₅ H X.436 CH₃ H CH₂Si(CH₃)₂CH(CH₃)₂ H X.437 CH₃ HCH₂Si(CH₃)₂OCH₃ H X.438 CH₃ H CH₂CH₂Si(CH₃)₂OCH₃ H X.439 CH₃ HCH(CH₃)Si(CH₃)₂OCH₃ H X.440 CH₃ H CH(CH₃)CH₂Si(CH₃)₂OCH₃ H X.441 CH₃ H2′-cyclopropyl-cyclopropyl H X.442 C₂H₅ H 2′-cyclopropyl-cyclopropyl HX.443 CH₂OCH₃ H 2′-cyclopropyl-cyclopropyl H X.444 CH₃ CH₂C≡CH2′-cyclopropyl-cyclopropyl H X.445 CH₃ H 2′-(α-CH₃-cyclopropyl)- Hcyclopropyl X.446 C₂H₅ H 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.447CH₂OCH₃ H 2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.448 CH₃ CH₂C≡CH2′-(α-CH₃-cyclopropyl)- H cyclopropyl X.449 CH₃ H2′-cyclobutyl-cyclopropyl H X.450 CH₃ H 2′-cyclopentyl-cyclopropyl HX.451 CH₃ H 2′-cyclohexyl-cyclopropyl H X.452 CH₃ H 4′-C≡CH-phenyl HX.453 C₂H₅ H 4′-C≡CH-phenyl H X.454 CH₃ H 4′-C≡C—Si(CH₃)₃-phenyl H X.455C₂H₅ H 4′-C≡C—Si(CH₃)₃-phenyl H X.456 CH₃ H 4′-C(H)═CH₂-phenyl H X.457C₂H₅ H 4′-C(H)═CH₂-phenyl H

Table 2 provides 457 compounds of formula (I-2):

wherein R², R³, R⁶ and R⁷ are as defined in Table 2.

Table 3 provides 457 compounds of formula (I-3):

wherein R², R³, R⁶ and R⁷ are as defined in Table 3.

Table 4 provides 457 compounds of formula (I-4):

wherein R², R³, R⁶ and R⁷ are as defined in Table 4.

Table 5 provides 457 compounds of formula (I-5):

wherein R², R³, R⁶ and R⁷ are as defined in Table 5.

Table 6 provides 457 compounds of formula (I-6):

wherein R², R³, R⁶ and R⁷ are as defined in Table 6.

Table 7 provides 457 compounds of formula (I-7):

wherein R², R³, R⁶ and R⁷ are as defined in Table 7.

Table Y represents Table 8 [when Y is 8], Table 9 [when Y is 9], Table10 [when Y is 10], Table 11 [when Y is 11], Table 12 [when Y is 12],Table 13 [when Y is 13], Table 14 [when Y is 14], Table 15 [when Y is15], Table 16 [when Y is 16], Table 17 [when Y is 17], Table 18 [when Yis 18] and represents Table 19 [when Y is 19].

TABLE Y Com- pound No. R² R³ R⁶ Y.001 CH₃ H phenyl Y.002 CH₃ CH₂C≡CHphenyl Y.003 CH₃ H 2′-fluorophenyl Y.004 CH₃ H 3′-fluorophenyl Y.005 CH₃H 4′-fluorophenyl Y.006 C₂H₅ H 4′-fluorophenyl Y.007 CH₂OCH₃ H4′-fluorophenyl Y.008 CH₃ COCH₃ 4′-fluorophenyl Y.009 CH₃ COCH₂OCH₃4′-fluorophenyl Y.010 CH₃ CH₂C≡CH 4′-fluorophenyl Y.011 CH₃ CH═C═CH₂4′-fluorophenyl Y.012 CH₃ COO-tert-Bu 4′-fluorophenyl Y.013 CH₃ H2′-chlorophenyl Y.014 CH₃ H 3′-chlorophenyl Y.015 CH₃ H 4′-chlorophenylY.016 C₂H₅ H 4′-chlorophenyl Y.017 CH₂OCH₃ H 4′-chlorophenyl Y.018 CH₃COCH₃ 4′-chlorophenyl Y.019 CH₃ COCH₂OCH₃ 4′-chlorophenyl Y.020 CH₃CH₂C≡CH 4′-chlorophenyl Y.021 CH₃ CH═C═CH₂ 4′-chlorophenyl Y.022 CH₃COO-tert-Bu 4′-chlorophenyl Y.023 CH₃ H 2′-bromophenyl Y.024 CH₃ H3′-bromophenyl Y.025 CH₃ H 4′-bromophenyl Y.026 C₂H₅ H 4′-bromophenylY.027 CH₂OCH₃ H 4′-bromophenyl Y.028 CH₃ COCH₃ 4′-bromophenyl Y.029 CH₃COCH₂OCH₃ 4′-bromophenyl Y.030 CH₃ CH₂C≡CH 4′-bromophenyl Y.031 CH₃CH═C═CH₂ 4′-bromophenyl Y.032 CH₃ COO-tert-Bu 4′-bromophenyl Y.033 CH₃ H2′-iodophenyl Y.034 CH₃ H 3′-iodophenyl Y.035 CH₃ H 4′-iodophenyl Y.036CH₃ H 2′-CF₃-phenyl Y.037 CH₃ H 3′-CF₃-phenyl Y.038 CH₃ H 4′-CF₃-phenylY.039 C₂H₅ H 4′-CF₃-phenyl Y.040 CH₂OCH₃ H 4′-CF₃-phenyl Y.041 CH₃ COCH₃4′-CF₃-phenyl Y.042 CH₃ COCH₂OCH₃ 4′-CF₃-phenyl Y.043 CH₃ CH₂C≡CH4′-CF₃-phenyl Y.044 CH₃ COO-tert-Bu 4′-CF₃-phenyl Y.045 CH₃ H2′-OCF₃-phenyl Y.046 CH₃ H 3′-OCF₃-phenyl Y.047 CH₃ H 4′-OCF₃-phenylY.048 C₂H₅ H 4′-OCF₃-phenyl Y.049 CH₂OCH₃ H 4′-OCF₃-phenyl Y.050 CH₃COCH₃ 4′-OCF₃-phenyl Y.051 CH₃ COCH₂OCH₃ 4′-OCF₃-phenyl Y.052 CH₃CH₂C≡CH 4′-OCF₃-phenyl Y.053 CH₃ COO-tert-Bu 4′-OCF₃-phenyl Y.054 CH₃CH═C═CH₂ 4′-OCF₃-phenyl Y.055 CH₃ H 4′-SCF₃-phenyl Y.056 CH₃ H2′-CH═NOH-phenyl Y.057 CH₃ H 3′-CH═NOH-phenyl Y.058 CH₃ H4′-CH═NOH-phenyl Y.059 CH₃ H 2′-CH═NOCH₃-phenyl Y.060 CH₃ H3′-CH═NOCH₃-phenyl Y.061 CH₃ H 4′-CH═NOCH₃-phenyl Y.062 CH₃ H2′-CH═NOC₂H₅-phenyl Y.063 CH₃ H 3′-CH═NOC₂H₅-phenyl Y.064 CH₃ H4′-CH═NOC₂H₅-phenyl Y.065 CH₃ H 2′-CN-phenyl Y.066 CH₃ H 3′-CN-phenylY.067 CH₃ H 4′-CN-phenyl Y.068 CH₃ H 2′-NO₂-phenyl Y.069 CH₃ H3′-NO₂-phenyl Y.070 CH₃ H 4′-NO₂-phenyl Y.071 CH₃ H 3′,4′-difluorophenylY.072 C₂H₅ H 3′,4′-difluorophenyl Y.073 CH₂OCH₃ H 3′,4′-difluorophenylY.074 CH₃ COCH₃ 3′,4′-difluorophenyl Y.075 CH₃ COCH₂OCH₃3′,4′-difluorophenyl Y.076 CH₃ CH₂C≡CH 3′,4′-difluorophenyl Y.077 CH₃COO-tert-Bu 3′,4′-difluorophenyl Y.078 CH₃ CH═C═CH₂ 3′,4′-difluorophenylY.079 CH₃ H 3′,4′-dichlorophenyl Y.080 C₂H₅ H 3′,4′-dichlorophenyl Y.081CH₂OCH₃ H 3′,4′-dichlorophenyl Y.082 CH₃ COCH₃ 3′,4′-dichlorophenylY.083 CH₃ COCH₂OCH₃ 3′,4′-dichlorophenyl Y.084 CH₃ CH₂C≡CH3′,4′-dichlorophenyl Y.085 CH₃ COO-tert-Bu 3′,4′-dichlorophenyl Y.086CH₃ CH═C═CH₂ 3′,4′-dichlorophenyl Y.087 CH₃ H 4′-chloro-3′-fluoro-phenylY.088 C₂H₅ H 4′-chloro-3′-fluoro-phenyl Y.089 CH₂OCH₃ H4′-chloro-3′-fluoro-phenyl Y.090 CH₃ COCH₃ 4′-chloro-3′-fluoro-phenylY.091 CH₃ COCH₂OCH₃ 4′-chloro-3′-fluoro-phenyl Y.092 CH₃ CH₂C≡CH4′-chloro-3′-fluoro-phenyl Y.093 CH₃ COO-tert-Bu4′-chloro-3′-fluoro-phenyl Y.094 CH₃ CH═C═CH₂ 4′-chloro-3′-fluoro-phenylY.095 CH₃ H 3′-chloro-4′-fluoro-phenyl Y.096 C₂H₅ H3′-chloro-4′-fluoro-phenyl Y.097 CH₂OCH₃ H 3′-chloro-4′-fluoro-phenylY.098 CH₃ COCH₃ 3′-chloro-4′-fluoro-phenyl Y.099 CH₃ COCH₂OCH₃3′-chloro-4′-fluoro-phenyl Y.100 CH₃ CH₂C≡CH 3′-chloro-4′-fluoro-phenylY.101 CH₃ COO-tert-Bu 3′-chloro-4′-fluoro-phenyl Y.102 CH₃ CH═C═CH₂3′-chloro-4′-fluoro-phenyl Y.103 CH₃ H 2′-4′-dichloro-phenyl Y.104CH₂OCH₃ H 2′-4′-dichloro-phenyl Y.105 CH₃ H 2′-4′-difluoro-phenyl Y.106CH₂OCH₃ H 2′-4′-difluoro-phenyl Y.107 CH₃ H CH₂CH₂CH₃ Y.108 C₂H₅ HCH₂CH₂CH₃ Y.109 CH₂OCH₃ H CH₂CH₂CH₃ Y.110 CH₃ CH₂C≡CH CH₂CH₂CH₃ Y.111CH₃ H CH₂CH₂CH₂CH₃ Y.112 C₂H₅ H CH₂CH₂CH₂CH₃ Y.113 CH₂OCH₃ HCH₂CH₂CH₂CH₃ Y.114 CH₃ CH₂C≡CH CH₂CH₂CH₂CH₃ Y.115 CH₃ H CH₂CH₂CH₂(C₂H₅)Y.116 C₂H₅ H CH₂CH₂CH₂(C₂H₅) Y.117 CH₂OCH₃ H CH₂CH₂CH₂(C₂H₅) Y.118 CH₃CH₂C≡CH CH₂CH₂CH₂(C₂H₅) Y.119 CH₃ H CH₂CH₂CH(CH₃)₂ Y.120 C₂H₅ HCH₂CH₂CH(CH₃)₂ Y.121 CH₂OCH₃ H CH₂CH₂CH(CH₃)₂ Y.122 CH₃ COCH₃CH₂CH₂CH(CH₃)₂ Y.123 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)₂ Y.124 CH₃ CH₂C≡CHCH₂CH₂CH(CH₃)₂ Y.125 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)₂ Y.126 CH₃ CH═C═CH₂CH₂CH₂CH(CH₃)₂ Y.127 CH₃ H CH₂CH₂CH(CH₃)(C₂H₅) Y.128 C₂H₅ HCH₂CH₂CH(CH₃)(C₂H₅) Y.129 CH₂OCH₃ H CH₂CH₂CH(CH₃)(C₂H₅) Y.130 CH₃ COCH₃CH₂CH₂CH(CH₃)(C₂H₅) Y.131 CH₃ COCH₂OCH₃ CH₂CH₂CH(CH₃)(C₂H₅) Y.132 CH₃CH₂C≡CH CH₂CH₂CH(CH₃)(C₂H₅) Y.133 CH₃ COO-tert-Bu CH₂CH₂CH(CH₃)(C₂H₅)Y.134 CH₃ CH═C═CH₂ CH₂CH₂CH(CH₃)(C₂H₅) Y.135 CH₃ H CH₂CH₂CH(C₂H₅)₂ Y.136C₂H₅ H CH₂CH₂CH(C₂H₅)₂ Y.137 CH₂OCH₃ H CH₂CH₂CH(C₂H₅)₂ Y.138 CH₃ COCH₃CH₂CH₂CH(C₂H₅)₂ Y.139 CH₃ COCH₂OCH₃ CH₂CH₂CH(C₂H₅)₂ Y.140 CH₃ CH₂C≡CHCH₂CH₂CH(C₂H₅)₂ Y.141 CH₃ COO-tert-Bu CH₂CH₂CH(C₂H₅)₂ Y.142 CH₃ CH═C═CH₂CH₂CH₂CH(C₂H₅)₂ Y.143 CH₃ H CH₂CH₂C(CH₃)₃ Y.144 C₂H₅ H CH₂CH₂C(CH₃)₃Y.145 CH₂OCH₃ H CH₂CH₂C(CH₃)₃ Y.146 CH₃ COCH₃ CH₂CH₂C(CH₃)₃ Y.147 CH₃COCH₂OCH₃ CH₂CH₂C(CH₃)₃ Y.148 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₃ Y.149 CH₃COO-tert-Bu CH₂CH₂C(CH₃)₃ Y.150 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)₃ Y.151 CH₃ HCH₂CH₂C(CH₃)₂(C₂H₅) Y.152 C₂H₅ H CH₂CH₂C(CH₃)₂(C₂H₅) Y.153 CH₂OCH₃ HCH₂CH₂C(CH₃)₂(C₂H₅) Y.154 CH₃ COCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) Y.155 CH₃COCH₂OCH₃ CH₂CH₂C(CH₃)₂(C₂H₅) Y.156 CH₃ CH₂C≡CH CH₂CH₂C(CH₃)₂(C₂H₅)Y.157 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)₂(C₂H₅) Y.158 CH₃ CH═C═CH₂CH₂CH₂C(CH₃)₂(C₂H₅) Y.159 CH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ Y.160 C₂H₅ HCH₂CH₂C(CH₃)(C₂H₅)₂ Y.161 CH₂OCH₃ H CH₂CH₂C(CH₃)(C₂H₅)₂ Y.162 CH₃ COCH₃CH₂CH₂C(CH₃)(C₂H₅)₂ Y.163 CH₃ COCH₂OCH₃ CH₂CH₂C(CH₃)(C₂H₅)₂ Y.164 CH₃CH₂C≡CH CH₂CH₂C(CH₃)(C₂H₅)₂ Y.165 CH₃ COO-tert-Bu CH₂CH₂C(CH₃)(C₂H₅)₂Y.166 CH₃ CH═C═CH₂ CH₂CH₂C(CH₃)(C₂H₅)₂ Y.167 CH₃ H CH(CH₃)CH₂CH₃ Y.168C₂H₅ H CH(CH₃)CH₂CH₃ Y.169 CH₂OCH₃ H CH(CH₃)CH₂CH₃ Y.170 CH₃ CH₂C≡CHCH(CH₃)CH₂CH₃ Y.171 CH₃ H CH(C₂H₅)CH₂CH₃ Y.172 C₂H₅ H CH(C₂H₅)CH₂CH₃Y.173 CH₂OCH₃ H CH(C₂H₅)CH₂CH₃ Y.174 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₃ Y.175CH₃ H CH(CF₃)CH₂CH₃ Y.176 C₂H₅ H CH(CF₃)CH₂CH₃ Y.177 CH₂OCH₃ HCH(CF₃)CH₂CH₃ Y.178 CH₃ CH₂C≡CH CH(CF₃)CH₂CH₃ Y.179 CH₃ HCH(CH₃)CH₂CH₂CH₃ Y.180 C₂H₅ H CH(CH₃)CH₂CH₂CH₃ Y.181 CH₂OCH₃ HCH(CH₃)CH₂CH₂CH₃ Y.182 CH₃ CH₂C≡CH CH(CH₃)CH₂CH₂CH₃ Y.183 CH₃ HCH(C₂H₅)CH₂CH₂CH₃ Y.184 C₂H₅ H CH(C₂H₅)CH₂CH₂CH₃ Y.185 CH₂OCH₃ HCH(C₂H₅)CH₂CH₂CH₃ Y.186 CH₃ CH₂C≡CH CH(C₂H₅)CH₂CH₂CH₃ Y.187 CH₃ HCH(CF₃)CH₂CH₂CH₃ Y.188 C₂H₅ H CH(CF₃)CH₂CH₂CH₃ Y.189 CH₃ HCH(CH₃)CH₂CH(CH₃)₂ Y.190 C₂H₅ H CH(CH₃)CH₂CH(CH₃)₂ Y.191 CH₂OCH₃ HCH(CH₃)CH₂CH(CH₃)₂ Y.192 CH₃ COCH₃ CH(CH₃)CH₂CH(CH₃)₂ Y.193 CH₃COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)₂ Y.194 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)₂ Y.195CH₃ COO-tert-Bu CH(CH₃)CH₂CH(CH₃)₂ Y.196 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)₂Y.197 CH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.198 C₂H₅ H CH(CH₃)CH₂CH(CH₃)(C₂H₅)Y.199 CH₂OCH₃ H CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.200 CH₃ COCH₃CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.201 CH₃ COCH₂OCH₃ CH(CH₃)CH₂CH(CH₃)(C₂H₅)Y.202 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.203 CH₃ COO-tert-BuCH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.204 CH₃ CH═C═CH₂ CH(CH₃)CH₂CH(CH₃)(C₂H₅) Y.205CH₃ H CH(CH₃)CH₂CH(C₂H₅)₂ Y.206 C₂H₅ H CH(CH₃)CH₂CH(C₂H₅)₂ Y.207 CH₂OCH₃H CH(CH₃)CH₂CH(C₂H₅)₂ Y.208 CH₃ COCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ Y.209 CH₃COCH₂OCH₃ CH(CH₃)CH₂CH(C₂H₅)₂ Y.210 CH₃ CH₂C≡CH CH(CH₃)CH₂CH(C₂H₅)₂Y.211 CH₃ COO-tert-Bu CH(CH₃)CH₂CH(C₂H₅)₂ Y.212 CH₃ CH═C═CH₂CH(CH₃)CH₂CH(C₂H₅)₂ Y.213 CH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ Y.214 C₂H₅ HCH(C₂H₅)CH₂CH(CH₃)₂ Y.215 CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)₂ Y.216 CH₃ COCH₃CH(C₂H₅)CH₂CH(CH₃)₂ Y.217 CH₃ COCH₂OCH₃ CH(C₂H₅)CH₂CH(CH₃)₂ Y.218 CH₃CH₂C≡CH CH(C₂H₅)CH₂CH(CH₃)₂ Y.219 CH₃ COO-tert-Bu CH(C₂H₅)CH₂CH(CH₃)₂Y.220 CH₃ CH═C═CH₂ CH(C₂H₅)CH₂CH(CH₃)₂ Y.221 CH₃ HCH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.222 C₂H₅ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.223CH₂OCH₃ H CH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.224 CH₃ CH₂C≡CHCH(C₂H₅)CH₂CH(CH₃)(C₂H₅) Y.225 CH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.226 C₂H₅ HCH(C₂H₅)CH₂CH(C₂H₅)₂ Y.227 CH₂OCH₃ H CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.228 CH₃CH₂C≡CH CH(C₂H₅)CH₂CH(C₂H₅)₂ Y.229 CH₃ H CH(CF₃)CH₂CH(CH₃)₂ Y.230 C₂H₅ HCH(CF₃)CH₂CH(CH₃)₂ Y.231 CH₂OCH₃ H CH(CF₃)CH₂CH(CH₃)₂ Y.232 CH₃ CH₂C≡CHCH(CF₃)CH₂CH(CH₃)₂ Y.233 CH₃ H CH(CF₃)CH₂CH(CH₃)(C₂H₅) Y.234 CH₃ HCH(CF₃)CH₂CH(C₂H₅)₂ Y.235 CH₃ H CH(CH₃)CH₂C(CH₃)₃ Y.236 C₂H₅ HCH(CH₃)CH₂C(CH₃)₃ Y.237 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₃ Y.238 CH₃ COCH₃CH(CH₃)CH₂C(CH₃)₃ Y.239 CH₃ COCH₂OCH₃ CH(CH₃)CH₂C(CH₃)₃ Y.240 CH₃CH₂C≡CH CH(CH₃)CH₂C(CH₃)₃ Y.241 CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₃ Y.242CH₃ CH═C═CH₂ CH(CH₃)CH₂C(CH₃)₃ Y.243 CH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.244C₂H₅ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.245 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)₂(C₂H₅)Y.246 CH₃ COCH₃ CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.247 CH₃ COCH₂OCH₃CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.248 CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.249CH₃ COO-tert-Bu CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.250 CH₃ CH═C═CH₂CH(CH₃)CH₂C(CH₃)₂(C₂H₅) Y.251 CH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.252 C₂H₅ HCH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.253 CH₂OCH₃ H CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.254CH₃ CH₂C≡CH CH(CH₃)CH₂C(CH₃)(C₂H₅)₂ Y.255 CH₃ H CH(C₂H₅)CH₂C(CH₃)₃ Y.256C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₃ Y.257 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₃ Y.258 CH₃CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₃ Y.259 CH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.260C₂H₅ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.261 CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅)Y.262 CH₃ CH₂C≡CH CH(C₂H₅)CH₂C(CH₃)₂(C₂H₅) Y.263 CH₃ HCH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.264 C₂H₅ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.265CH₂OCH₃ H CH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.266 CH₃ CH₂C≡CHCH(C₂H₅)CH₂C(CH₃)(C₂H₅)₂ Y.267 CH₃ H CH(CF₃)CH₂C(CH₃)₃ Y.268 C₂H₅ HCH(CF₃)CH₂C(CH₃)₃ Y.269 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₃ Y.270 CH₃ CH₂C≡CHCH(CF₃)CH₂C(CH₃)₃ Y.271 CH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.272 C₂H₅ HCH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.273 CH₂OCH₃ H CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.274CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)₂(C₂H₅) Y.275 CH₃ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂Y.276 C₂H₅ H CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.277 CH₂OCH₃ HCH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.278 CH₃ CH₂C≡CH CH(CF₃)CH₂C(CH₃)(C₂H₅)₂ Y.279CH₃ H 2′-tert-butyl-cyclopropyl Y.280 C₂H₅ H 2′-tert-butyl-cyclopropylY.281 CH₂OCH₃ H 2′-tert-butyl-cyclopropyl Y.282 CH₃ CH₂C≡CH2′-tert-butyl-cyclopropyl Y.283 CH₃ H 2′-isobutyl-cyclopropyl Y.284 C₂H₅H 2′-isobutyl-cyclopropyl Y.285 CH₂OCH₃ H 2′-isobutyl-cyclopropyl Y.286CH₃ CH₂C≡CH 2′-isobutyl-cyclopropyl Y.287 CH₃ H4′,4′-dimethyl-cyclobutyl Y.288 C₂H₅ H 4′,4′-dimethyl-cyclobutyl Y.289CH₂OCH₃ H 4′,4′-dimethyl-cyclobutyl Y.290 CH₃ CH₂C≡CH4′,4′-dimethyl-cyclobutyl Y.291 CH₃ H cyclopentyl Y.292 C₂H₅ Hcyclopentyl Y.293 CH₂OCH₃ H cyclopentyl Y.294 CH₃ CH₂C≡CH cyclopentylY.295 CH₃ H 3′-methyl-cyclopentyl Y.296 C₂H₅ H 3′-methyl-cyclopentylY.297 CH₂OCH₃ H 3′-methyl-cyclopentyl Y.298 CH₃ CH₂C≡CH3′-methyl-cyclopentyl Y.299 CH₃ H cyclohexyl Y.300 C₂H₅ H cyclohexylY.301 CH₂OCH₃ H cyclohexyl Y.302 CH₃ CH₂C≡CH cyclohexyl Y.303 CH₃ H3′-methyl-cyclohexyl Y.304 C₂H₅ H 3′-methyl-cyclohexyl Y.305 CH₂OCH₃ H3′-methyl-cyclohexyl Y.306 CH₃ CH₂C≡CH 3′-methyl-cyclohexyl Y.307 CH₃ H4′-methyl-cyclohexyl Y.308 C₂H₅ H 4′-methyl-cyclohexyl Y.309 CH₂OCH₃ H4′-methyl-cyclohexyl Y.310 CH₃ CH₂C≡CH 4′-methyl-cyclohexyl Y.311 CH₃ Hcycloheptyl Y.312 C₂H₅ H cycloheptyl Y.313 CH₂OCH₃ H cycloheptyl Y.314CH₃ CH₂C≡CH cycloheptyl Y.315 CH₃ H 2′-thienyl Y.316 C₂H₅ H 2′-thienylY.317 CH₂OCH₃ H 2′-thienyl Y.318 CH₃ CH₂C≡CH 2′-thienyl Y.319 CH₃ H3′-thienyl Y.320 C₂H₅ H 3′-thienyl Y.321 CH₂OCH₃ H 3′-thienyl Y.322 CH₃CH₂C≡CH 3′-thienyl Y.323 CH₃ H 5′-chloro-2′-thienyl Y.324 C₂H₅ H5′-chloro-2′-thienyl Y.325 CH₂OCH₃ H 5′-chloro-2′-thienyl Y.326 CH₃CH₂C≡CH 5′-chloro-2′-thienyl Y.327 CH₃ H 2′-furyl Y.328 C₂H₅ H 2′-furylY.329 CH₂OCH₃ H 2′-furyl Y.330 CH₃ CH₂C≡CH 2′-furyl Y.331 CH₃ H5′-chloro-2′-furyl Y.332 C₂H₅ H 5′-chloro-2′-furyl Y.333 CH₂OCH₃ H5′-chloro-2′-furyl Y.334 CH₃ CH₂C≡CH 5′-chloro-2′-furyl Y.335 CH₃ H2′-pyridyl Y.336 C₂H₅ H 2′-pyridyl Y.337 CH₂OCH₃ H 2′-pyridyl Y.338 CH₃CH₂C≡CH 2′-pyridyl Y.339 CH₃ H 3′-pyridyl Y.340 C₂H₅ H 3′-pyridyl Y.341CH₂OCH₃ H 3′-pyridyl Y.342 CH₃ CH₂C≡CH 3′-pyridyl Y.343 CH₃ H 4′-pyridylY.344 C₂H₅ H 4′-pyridyl Y.345 CH₂OCH₃ H 4′-pyridyl Y.346 CH₃ CH₂C≡CH4′-pyridyl Y.347 CH₃ H 6′-chloro-3′-pyridyl Y.348 C₂H₅ H6′-chloro-3′-pyridyl Y.349 CH₂OCH₃ H 6′-chloro-3′-pyridyl Y.350 CH₃CH₂C≡CH 6′-chloro-3′-pyridyl Y.351 CH₃ H 6′-fluoro-3′-pyridyl Y.352 C₂H₅H 6′-fluoro-3′-pyridyl Y.353 CH₂OCH₃ H 6′-fluoro-3′-pyridyl Y.354 CH₃CH₂C≡CH 6′-fluoro-3′-pyridyl Y.355 CH₃ H 6′-bromo-3′-pyridyl Y.356 C₂H₅H 6′-bromo-3′-pyridyl Y.357 CH₂OCH₃ H 6′-bromo-3′-pyridyl Y.358 CH₃CH₂C≡CH 6′-bromo-3′-pyridyl Y.359 CH₃ H 2′-oxazolyl Y.360 CH₃ H3′-isoxazolyl Y.361 CH₃ H CH(CH₃)₂ Y.362 C₂H₅ H CH(CH₃)₂ Y.363 CH₂OCH₃ HCH(CH₃)₂ Y.364 CH₃ CH₂C≡CH CH(CH₃)₂

Table 8 provides 364 compounds of formula (I-8):

wherein R², R³, and R⁶ are as defined in Table 8.

Table 9 provides 364 compounds of formula (I-9):

wherein R², R³, and R⁶ are as defined in Table 9.

Table 10 provides 364 compounds of formula (I-10):

wherein R², R³, and R⁶ are as defined in Table 10.

Table 11 provides 364 compounds of formula (I-11):

wherein R², R³, and R⁶ are as defined in Table 11.

Table 12 provides 364 compounds of formula (I-12):

wherein R², R³, and R⁶ are as defined in Table 12.

Table 13 provides 364 compounds of formula (I-13):

wherein R², R³, and R⁶ are as defined in Table 13.

Table 14 provides 364 compounds of formula (I-14):

wherein R², R³, and R⁶ are as defined in Table 14.

Table 15 provides 364 compounds of formula (I-15):

wherein R², R³, and R⁶ are as defined in Table 15.

Table 16 provides 364 compounds of formula (I-16):

wherein R², R³, and R⁶ are as defined in Table 16.

Table 17 provides 364 compounds of formula (I-17):

wherein R², R³, and R⁶ are as defined in Table 17.

Table 18 provides 364 compounds of formula (I-18):

wherein R², R³, and R⁶ are as defined in Table 18.

Table 19 provides 364 compounds of formula (I-19):

wherein R², R³, and R⁶ are as defined in Table 19.

Table Z represents Table 20 [when Z is 20], Table 21 [when Z is 21],Table 22 [when Z is 22], Table 23 [when Z is 23], Table 24 [when Z is24] and represents Table 25 [when Z is 25].

TABLE Z Com- pound No. R² R³ A Z.001 CH₃ H

Z.002 C₂H₅ H

Z.003 CH₃OCH₃ H

Z.004 CH₃ CH₂C≡CH

Z.005 CH₃ H

Z.006 C₂H₅ H

Z.007 CH₂OCH₃ H

Z.008 CH₃ CH₂C≡CH

Z.009 CH₃ H

Z.010 C₂H₅ H

Z.011 CH₂OCH₃ H

Z.012 CH₃ CH₂C≡CH

Z.013 CH₃ H

Z.014 C₂H₅ H

Z.015 CH₂OCH₃ H

Z.016 CH₃ CH₂C≡CH

Z.017 CH₃ H

Z.018 C₂H₅ H

Z.019 CH₂OCH₃ H

Z.020 CH₃ CH₂C≡CH

Z.021 CH₃ H

Z.022 C₂H₅ H

Z.023 CH₂OCH₃ H

Z.024 CH₃ CH₂C≡CH

Z.025 CH₃ H

Z.026 C₂H₅ H

Z.027 CH₂OCH₃ H

Z.028 CH₃ CH₂C≡CH

Z.029 CH₃ H

Z.030 C₂H₅ H

Z.031 CH₂OCH₃ H

Z.032 CH₃ CH₂C≡CH

Z.033 CH₃ H

Z.034 C₂H₅ H

Z.035 CH₂OCH₃ H

Z.036 CH₃ CH₂C≡CH

Z.037 CH₃ H

Z.038 C₂H₅ H

Z.039 CH₂OCH₃ H

Z.040 CH₃ CH₂C≡CH

Z.041 CH₃ H

Z.042 C₂H₅ H

Z.043 CH₂OCH₃ H

Z.044 CH₃ CH₂C≡CH

Z.045 CH₃ H

Z.046 C₂H₅ H

Z.047 CH₂OCH₃ H

Z.048 CH₃ CH₂C≡CH

Z.049 CH₃ H

Z.050 C₂H₅ H

Z.051 CH₂OCH₃ H

Z.052 CH₃ CH₂C≡CH

Z.053 CH₃ H

Z.054 C₂H₅ H

Z.055 CH₂OCH₃ H

Z.056 CH₃ CH₂C≡CH

Z.057 CH₃ H

Z.058 C₂H₅ H

Z.059 CH₂OCH₃ H

Z.060 CH₃ CH₂C≡CH

Z.061 CH₃ H

Z.062 C₂H₅ H

Z.063 CH₂OCH₃ H

Z.064 CH₃ CH₂C≡CH

Z.065 CH₃ H

Z.066 C₂H₅ H

Z.067 CH₂OCH₃ H

Z.068 CH₃ CH₂C≡CH

Z.069 CH₃ H

Z.070 C₂H₅ H

Z.071 CH₂OCH₃ H

Z.072 CH₃ CH₂C≡CH

Z.073 CH₃ H

Z.074 C₂H₅ H

Z.075 CH₂OCH₃ H

Z.076 CH₃ CH₂C≡CH

Z.077 CH₃ H

Z.078 C₂H₅ H

Z.079 CH₂OCH₃ H

Z.080 CH₃ CH₂C≡CH

Z.081 CH₃ H

Z.082 C₂H₅ H

Z.083 CH₂OCH₃ H

Z.084 CH₃ CH₂C≡CH

Z.085 CH₃ H

Z.086 C₂H₅ H

Z.087 CH₂OCH₃ H

Z.088 CH₃ CH₂C≡CH

Z.089 CH₃ H

Z.090 C₂H₅ H

Z.091 CH₂OCH₃ H

Z.092 CH₃ CH₂C≡CH

Z.093 CH₃ H

Z.094 C₂H₅ H

Z.095 CH₂OCH₃ H

Z.096 CH₃ CH₂C≡CH

Z.097 CH₃ H

Z.098 C₂H₅ H

Z.099 CH₂OCH₃ H

Z.100 CH₃ CH₂C≡CH

Z.101 CH₃ H

Z.102 C₂H₅ H

Z.103 CH₂OCH₃ H

Z.104 CH₃ CH₂C≡CH

Z.105 CH₃ H

Z.106 CH₃ H

Z.107 CH₃ H

Z.108 CH₃ H

Z.109 CH₃ H

Z.110 CH₃ H

Z.111 CH₃ H

Z.112 CH₃ H

Z.113 CH₃ H

Z.114 CH₃ H

Z.115 CH₃ H

Z.116 C₂H₅ H

Z.117 CH₂OCH₃ H

Z.118 CH₃ CH₂C≡CH

Z.119 CH₃ H

Z.120 CH₃ H

Z.121 C₂H₅ H

Z.122 CH₂OCH₃ H

Z.123 CH₃ CH₂C≡CH

Z.124 CH₃ H

Z.125 CH₃ H

Z.126 CH₃ H

Z.127 CH₃ H

Z.128 CH₃ H

Z.129 CH₃ H

Z.130 CH₃ H

Z.131 CH₃ H

Z.132 C₂H₅ H

Z.133 CH₂OCH₃ H

Z.134 CH₃ CH₂C≡CH

Z.135 CH₃ H

Z.136 CH₃ H

Z.137 C₂H₅ H

Z.138 CH₂OCH₃ H

Z.139 CH₃ CH₂C≡CH

Z.140 CH₃ H

Z.141 CH₃ H

Z.142 CH₃ H

Z.143 CH₃ H

Z.144 CH₃ H

Z.145 CH₃ H

Z.146 CH₃ H

Z.147 CH₃ H

Z.148 CH₃ H

Z.149 CH₃ H

Z.150 CH₃ H

Z.151 CH₃ H

Z.152 CH₃ H

Z.153 CH₃ H

Z.154 CH₃ H

Z.155 CH₃ H

Z.156 CH₃ H

Z.157 CH₃ H

Z.158 CH₃ H

Z.159 CH₃ H

Z.160 CH₃ H

Z.161 CH₃ H

Z.162 CH₃ H

Z.163 CH₃ H

Z.164 CH₃ H

Z.165 CH₃ H

Z.166 CH₃ H

Z.167 CH₃ H

Z.168 CH₃ H

Z.169 CH₃ H

Z.170 CH₃ H

Z.171 CH₃ H

Z.172 CH₃ H

Z.173 CH₃ H

Z.174 CH₃ H

Z.175 CH₃ H

Z.176 CH₃ H

Z.177 CH₃ H

Z.178 CH₃ H

Z.179 CH₃ H

Z.180 CH₃ H

Z.181 CH₃ H

Z.182 CH₃ H

Table 20 provides 182 compounds of formula (I-20):

wherein R², R³ and A are as defined in Table 20.

Table 21 provides 182 compounds of formula (I-21):

wherein R², R³ and A are as defined in Table 21.

Table 22 provides 182 compounds of formula (I-22):

wherein R², R³ and A are as defined in Table 22.

Table 23 provides 182 compounds of formula (I-23):

wherein R², R³ and A are as defined in Table 23.

Table 24 provides 182 compounds of formula (I-24):

wherein R², R³ and A are as defined in Table 24.

Table 25 provides 182 compounds of formula (I-25):

wherein R², R³ and A are as defined in Table 25.

Table 26 provides 133 compounds of formula (IIIa) where R¹³, R¹⁴, R¹⁵,R¹⁶, Q and X are as defined in Table 26. Q is shown to be either asingle bond (—) or a double bond (═).

TABLE 26 Compound. No. R¹³ R¹⁴ R¹⁵ R¹⁶ Q X 26.001 CH₃ CH₃ H H ═ O 26.002CH₃ H H H ═ O 26.003 H CH₃ H H ═ O 26.004 CH₃ CH₃ C(O)CH₃ H ═ O 26.005CH₃ CH₃ H C(O)CH₃ ═ O 26.006 CH₃ C(O)CH₃ H H ═ O 26.007 H H H H ═ O26.008 CF₃ CF₃ H H ═ O 26.009 OCH₃ OCH₃ H H ═ O 26.010 H H CH₃ CH₃ ═ O26.011 C₂H₅ C₂H₅ H H ═ O 26.012 CH₃ H CH₃ H ═ O 26.013 H CH₃ H CH₃ ═ O26.014 CH₃ CH₃ H H — O 26.015 CH₃ H H H — O 26.016 H CH₃ H H — O 26.017CH₃ CH₃ C(O)CH₃ H — O 26.018 CH₃ CH₃ H C(O)CH₃ — O 26.019 CH₃ C(O)CH₃ HH — O 26.020 H H H H — O 26.021 CF₃ CF₃ H H — O 26.022 OCH₃ OCH₃ H H — O26.023 H H CH₃ CH₃ — O 26.024 C₂H₅ C₂H₅ H H — O 26.025 CH₃ H CH₃ H — O26.026 H H H H — CH₂ 26.027 CH₃ H CH₃ H — CH₂ 26.028 CH₃ H CH₃ H ═ CH₂26.029 H CH₃ H CH₃ — CH₂ 26.030 H CH₃ H CH₃ ═ CH₂ 26.031 CH₃ CH₃ CH₃ CH₃═ CH₂ 26.032 CH₃ CH₃ CH₃ CH₃ — CH₂ 26.033 CH₃ CH₃ CH₃ CH₃ ═ CH(CH₃) synor anti 26.034 CH₃ CH₃ CH₃ CH₃ — CH(CH₃) syn or anti 26.035 H H H H ═CH(CH₃) syn or anti 26.036 H H H H — CH(CH₃) syn or anti 26.037 H H H H— CH(C₂H₅) syn or anti 26.038 H H H H — CH₂CH₂ 26.039 CH₃ CH₃ H H ═CH₂CH₂ 26.040 CH₃ CH₃ H H — CH₂CH₂ 26.041 H H CH₃ CH₃ ═ CH₂CH₂ 26.042 HH CH₃ CH₃ — CH₂CH₂ 26.043 H H OCH₃ H — CH₂CH₂ 26.044 H H H OCH₃ — CH₂CH₂26.045 H H H H — CH₂CH₂CH₂ 26.046 H H H H ═ CH₂CH₂CH₂ 26.047 H H CH₃ CH₃═ C(CH₃)₂ 26.048 H H CH₃ CH₃ — C(CH₃)₂ 26.049 CH₃ CH₃ CH₃ CH₃ ═ C(CH₃)₂26.050 CH₃ CH₃ CH₃ CH₃ — C(CH₃)₂ 26.051 CH₃ H CH₃ H — C(CH₃)₂ 26.052 HCH₃ H CH₃ — C(CH₃)₂ 26.053 CH₃ H CH₃ H ═ C(CH₃)₂ 26.054 H CH₃ H CH₃ ═C(CH₃)₂ 26.055 CH₃ CH₃ CH₃ CH₃ — C(CH₃)(C₂H₅) 26.056 H H H H — C(CH₃)₂26.057 H H H H ═ C(CH₃)₂ 26.058 CH₃ CH₃ H H — C(CH₃)₂ 26.059 CH₃ CH₃ H H═ C(CH₃)₂ 26.060 H H H H ═ C(OCH₃)₂ 26.061 H H H H — CH(OCH₃) 26.062 H HH H ═ S 26.063 H H H H — S 26.064 CH₃ CH₃ H H ═ S 26.065 CH₃ CH₃ H H — S26.066 H H CH₃ CH₃ ═ S 26.067 H H CH₃ CH₃ — S 26.068 OCH₃ OCH₃ H H ═ S26.069 OCH₃ OCH₃ H H — S 26.070 H CH₃ H H ═ S 26.071 H CH₃ H H — S26.072 CH₃ H H H ═ S 26.073 CH₃ H H H — S 26.074 CH₃ H CH₃ H ═ S 26.075CH₃ H CH₃ H — S 26.076 H CH₃ H CH₃ ═ S 26.077 H CH₃ H CH₃ — S 26.078 HOCH₃ H H ═ S 26.079 H OCH₃ H H — S 26.080 OCH₃ H H H ═ S 26.081 OCH₃ H HH — S 26.082 CH₃ H CH₃ CH₃ ═ S 26.083 CH₃ H CH₃ CH₃ — S 26.084 H CH₃ CH₃CH₃ ═ S 26.085 H CH₃ CH₃ CH₃ — S 26.086 H H CH₃ H ═ S 26.087 H H CH₃ H —S 26.088 H H H CH₃ ═ S 26.089 H H H CH₃ — S 26.090 H H OCH₃ H ═ S 26.091H H OCH₃ H — S 26.092 H H H OCH₃ ═ S 26.093 H H H OCH₃ — S 26.094 H H HH ═ N(CH₃) 26.095 H H H H — N(CH₃) 26.096 CH₃ CH₃ H H ═ N(CH₃) 26.097CH₃ CH₃ H H — N(CH₃) 26.098 H H H H ═ N(C₂H₅) 26.099 H H H H — N(C₂H₅)26.100 H H H H — NH 26.101 H H H H — NC(O)OC(CH₃)₃ 26.102 CH₃ CH₃ H H —NC(O)OC(CH₃)₃ 26.103 H H H H — N(CHO) 26.104 H H H H — N(C(O)CH₃) 26.105CH₃ CH₃ H H — N(C(O)CH₃ 26.106 H H H H — N(C(O)OCH₃) 26.107 CH₃ CH₃ H H— N(C(O)OCH₃) 26.108 H H H H — N(C(O)OC₂H₅) 26.109 CH₃ CH₃ H H —N(C(O)OC₂H₅) 26.110 H H H H — N(C(O)OCH₂CH₂Cl) 26.111 CH₃ CH₃ H H —N(C(O)OCH₂CH₂Cl) 26.112 H H H H — N(C(O)OC₄H₉-(n) 26.113 CH₃ CH₃ H H —N(C(O)OC₄H₉-(n) 26.114 H H H H — N(C(O)OC₄H₉-(i) 26.115 CH₃ CH₃ H H —N(C(O)OC₄H₉-(i) 26.116 H H H H — CH(C₃H₇-(i)) syn or anti 26.117 H H H H— CH(C₃H₇-(n)) syn or anti 26.118 H H H H — CH(C₄H₉-(i)) syn or anti26.119 H H H H — C(C₂H₄-(c)) 26.120 H H H H — C(C₄H₈-(c)) 26.121 H H H H— CHCH(C₂H₅)₂ syn or anti 26.122 H H H H — CHCH₂(C₃H₅-(c)) syn or anti26.123 H H H H — CH(C₅H₉-(c)) syn or anti 26.124 H H H H —CHCH₂OC(═O)CH₃ syn or anti 26.125 H H H H — CH(CH═O) syn or anti 26.126H H H H — CHCH₂OH 26.127 H H H H — C(OC₃H₇-(n))2 26.128 H H H H — C═O26.129 H H H H — CHCH₂—C₆H₅ syn or anti 26.130 H H H H — C═C(CH₃)₂26.131 H H H H — C═C(C₂H₅)₂ 26.132 H H H H — cyclopentylidene 26.133 H HH H — C(CH₃)(C₂H₅) In either configuration

Table ZZ represents Table 27 (when ZZ is 27) and represents Table 28(when ZZ is 28).

TABLE ZZ Compound No. R³ R⁶ R² R¹ ZZ.1 H SiMe₃ Me CF₃ ZZ.2 H SiMe₃ MeCF₂H ZZ.3 H CH₂SiMe₃ Me CF₃ ZZ.4 H CH₂SiMe₃ Me CF₂H ZZ.5 propargylCH₂SiMe₃ Me CF₃ ZZ.6 H CHMeSiMe₃ Me CF₃ ZZ.7 H CHMeSiMe₃ Me CF₂H ZZ.8propargyl CHMeSiMe₃ Me CF₃ ZZ.9 allenyl CHMeSiMe₃ Me CF₃ ZZ.10 COMeCHMeSiMe₃ Me CF₃ ZZ.11 H CHMeSiMe₃ Me Me ZZ.12 H (CH₂)₂SiMe₃ Me CF₃ZZ.13 H (CH₂)₂SiMe₃ Me CF₂H ZZ.14 propargyl (CH₂)₂SiMe₃ Me CF₃ ZZ.15 H(CH₂)₂SiMe₃ Me Me ZZ.16 H (CH₂)₂SiMe₃ CF₃ CF₃ ZZ.17 H CHMeCH₂SiMe₃ MeCF₃ ZZ.18 H CHMeCH₂SiMe₃ Me CF₂H ZZ.19 propargyl CHMeCH₂SiMe₃ Me CF₃ZZ.20 propargyl CHMeCH₂SiMe₃ Me CF₂H ZZ.21 H CHMeCH₂SiMe₃ Me Me ZZ.22 HCHMeCH₂SiMe₃ CF₃ CF₃ ZZ.23 COMe CHMeCH₂SiMe₃ Me CF₃ ZZ.24 H (CH₂)₃SiMe₃Me CF₃ ZZ.25 H (CH₂)₃SiMe₃ Me CF₂H ZZ.26 H CH₂Si(Me₂)Et Me CF₃ ZZ.27 HCH₂Si(Me₂)Et Me CF₂H ZZ.28 H CH₂Si(Me₂)CHMe₂ Me CF₃ ZZ.29 HCH₂Si(Me₂)CHMe₂ Me CF₂H ZZ.30 H CH₂CHMeSiMe₃ Me CF₃ ZZ.31 H CH₂CHMeSiMe₃Me CF₂H ZZ.32 H CMe₂CH₂SiMe₃ Me CF₃ ZZ.33 H CMe₂CH₂SiMe₃ Me CF₂H ZZ.34 HCHMeCHMeSiMe₃ Me CF₂H ZZ.35 H CHMeCHMeSiMe₃ Me CF₃ ZZ.36 H CH₂CMe₂SiMe₃Me CF₃ ZZ.37 H CH₂CMe₂SiMe₃ Me CF₂H ZZ.38 H CHMe(CH₂)₂SiMe₃ Me CF₂HZZ.39 H CHMe(CH₂)₂SiMe₃ Me CF₃ ZZ.40 H (CH₂)₂SiMe₃ CH₂OMe CH₂Me ZZ.41 H(CH₂)₂SiMe₃ CH₂OCH₂Me CH₂Me ZZ.42 H SiMe₂CH₂CHMe₂ Me CF₃

Table 27 provides 42 compounds of formula (I-27) where R¹, R², R³ and R⁶are as defined in Table 9.

Table 28 provides 42 compounds of formula (I-28) where R¹, R², R³ and R⁶are as defined in Table 10.

Throughout this description, temperatures are given in degrees Celsius;“NMR” means nuclear magnetic resonance spectrum; MS stands for massspectrum; “%” is percent by weight, unless corresponding concentrationsare indicated in other units; “syn” refers to a syn configuration of therelevant substituent with respect to the anellated benzene ring; and“anti” refers to an anti configuration of the relevant substituent withrespect to the anellated benzene ring.

The following abbreviations are used throughout this description:

m.p.=melting point b.p.=boiling point.

s=singlet br=broad

d=doublet dd=doublet of doublets

t=triplet q=quartet

m=multiplet ppm=parts per million

Table 29 shows selected melting point data for compounds of Tables 1 to28.

TABLE 29 Compound No. m.p./(° C.) 1.03 56-57 1.13 176-177 1.15 liquid1.50 64-66 2.005 146-147 2.017 148 2.029 148-149 2.067 165-166 2.070139-142 2.219 94.6-95.4 2.273 125-126 2.321 124-125 2.411 117-118 2.427103-105 2.423 105 2.445 (trans) 98-99 2.452 123-125 2.454 161-163 2.456122-123 3.005 143-145 3.017 155-156 3.029 154-155 3.067 144-145 3.070136-137 3.219 71-73 3.273 87-88 3.321 121-122 3.407 83-85 3.411 91-933.427 75-76 3.423 121-122 3.445 94-95 3.452 161-162 3.454 144-145 3.456133-135 4.017 158-159 4.273 89-91 4.411 84-86 4.445 84-85 4.452 143-1444.456 122-124 8.189 104-106 9.189 82-83 20.017 167-169 20.021 121-12220.065 144-145 20.073 157-158 20.097 108-109 20.101 155-157 20.115137-139 20.120 160-161 20.147 159-162 (decomposition) 20.148 133-13920.149 amorphous 20.161 amorphous 20.166 (syn:anti 90:10) 150-153 20.166(syn:anti 34:66) 111-116 20.168 (syn:anti 40:60) 102-120 20.169(syn:anti 86:14) 105-109 20.170 (syn:anti 74:26) amorphous 20.171(syn:anti 16:84) 106-107 20.171 (syn:anti 81:19) amorphous 20.176(syn:anti 80:20) 126-129 20.179 187-189 20.180 109-110 21.097 107-10921.101 120-122 21.017 175-177 21.021 125-126 21.065 114-116 21.073135-137 21.105 140-143 21.114 189-191 21.115 164-166 21.120 172-17521.148 134-136 21.152 170-172 21.153 amorphous 21.154 120-122 21.155amorphous 21.161 amorphous 21.165 (syn) 106-108 21.166 (syn:anti 90:10)148-149 22.101 97-98 22.115 135-138 22.147 viscous 22.148 130-132 22.149amorphous 22.161 amorphous 26.001 92-96 26.007 121-124 26.014 92-9326.015 115-116 26.016 92-93 26.020 75-76 26.026 63-64 26.038 74-7526.095 139-140 26.099 viscous 26.100 viscous 26.101 89-90 26.102 94-9526.103 176-177 26.105 110-111 26.106 104-105 26.107 114-115 26.108viscous 26.110 viscous 26.112 viscous 26.114 viscous 26.116 (syn:anti86:14) waxy solid 26.116 (syn:anti 35:65) oil 26.118 (syn:anti 10:90)viscous 26.118 (syn:anti 82:18) viscous 26.119 oil 26.121 (syn:anti50:50) oil 26.122 (syn:anti 84:14) oil 26.123 (syn:anti 75:25) 73-7826.128 (syn:anti 74:26) oil 26.129 81-82 26.130 oil

The compounds according to formula (I) may be prepared according to thefollowing reaction schemes.

(a) Preparation of a Compound of Formula (II).

Schemes 1, 2 and 3 demonstrate that a compound of formula E, H, K, L, N,O, P, R, S, T, U, V, W, Y or Z [where R¹ and R² are as defined above forformula (II); and R′ is C₁₋₅ alkyl] {each of which is a compound offormula (II), as defined above} may be prepared by a reaction sequencestarting with a 1,2,3-triazole-4,5-dicarboxylic acid diester of formulaA [Y. Tanaka et al., Tetrahedron, 29, 3271 (1973)] [where each R′ is,independently, C₁₋₅ alkyl] (preferably the dimethyl ester).

Treatment of A with an alkylating agent [such as R²-halo (where R² is asdefined above for formula (II); and halo is preferably iodo) or anappropriate sulphate, sulphonate or carbonate ester] in the presence ofa base [such as K₂CO₃, Na₂CO₃ or NEt₃] in a suitable solvent [such asacetonitrile, DMF or dimethylacetamide] at ambient to elevatedtemperatures furnishes a mixture of regioisomers, of formulae B and C,which may be separated by conventional methods. Saponification of acompound of formula B with up to one equivalent of a base [such as KOH,NaOH or LiOH] in a protic solvent [such as methanol], preferably underreflux conditions, provides a mono-ester of formula D. Subsequentreaction of a compound of formula D with a fluorinating agent [such asDAST (diethylamino sulphur trifloride) or, preferably, SF₄] in thepresence of hydrofluoric acid gives a 5-CF₃-1,2,3-triazole-4-carboxylicacid ester of formula E.

Alternatively, treatment of a compound of formula D with a chlorinatingagent [such as thionyl chloride or phosgene] under standard conditionsresults in an acid chloride of formula F which may be reducedcatalytically in an inert solvent [for example ethyl acetate or THF] inthe presence of a base [for example Hünig base] to give analdehyde-ester of formula G (modified Rosenmund conditions).Fluorination of a compound of formula G by means of DAST, dimethoxy-DASTor SF₄ in the presence of hydrofluoric acid, optionally with solvent,preferably at elevated temperatures, forms a5-difluoromethyl-1,2,3-triazole-4-carboxylic acid ester of formula H.

Metal hydride reduction of a compound of formula G [for example by NaBH₄or LiBH₄] in methanol provides a 5-hydroxymethyl-1,2,3-triazole offormula J, from which a 5-fluoromethyl derivative of formula K may beobtained by fluorination under mild conditions, preferably with DAST atlow temperatures (0 to −78° C.) in an inert solvent [such asdichloromethane].

Alternatively, hydride reduction of a compound of formula J byconventional methods [for example via its mesylate, tosylate or iodide]results in a 5-methyl-1,2,3-triazole of formula L.

Chlorination of compound of formula D [for example by thionyl chloride]followed by treatment with ammonia, preferably in a protic solvent [suchas water, methanol or ethanol] furnishes an amide of formula M fromwhich a 5-cyano-1,2,3-triazole of formula N may be obtained by means ofa dehydrating agent [such as phosphorylchloride].

Further transformations to prepare a compound of formula (II) [where R¹and R² are as defined above for formula (I); Y is OR′ and R′ is C₁₋₅alkyl] include a Hofmann rearrangement of an amide of formula M withNaOBr or NaOCl in the presence of NaOH to give a 5-amino-1,2,3-triazoleof formula O.

Diazotation of a compound of formula O by means of sodium nitrite underaqueous acidic conditions [for example sulphuric acid] or with a nitriteester [for example (i)-amyl nitrite] in an organic solvent [for exampleacetone, dichloromethane or THF] in the presence of a halogenide [suchas CuCl or CuBr] gives a 5-halo-1,2,3-triazole of formula P [where halois Cl or Br] which on treatment with a fluorinating agent [such as KF orCsF], preferably in DMF or N-methylpyrrolidone at elevated temperatures,results in a 5-fluoro-1,2,3-triazole of formula V.

By diazotation of a compound of formula O and subsequent acidic aqueoushydrolysis under heating, a 5-hydroxy-1,2,3-triazole of formula Q may beobtained. Treatment of a compound of formula Q with an alkylating agent[such as methyl iodide, dimethylsulphate or dimethylcarbonate] and abase [for example NaH, K₂CO₃ or Na₂CO₃] in a polar solvent [for exampleDMF, DMSO or CH₃CN] gives a 5-methoxy-1,2,3-triazole of formula R whichmay be converted to a trichloromethoxy derivative of formula S with achlorinating agent [such as chlorine] in the presence ofazoisobutyronitrile (AIBN) or ultra-violet irradiation at elevatedtemperature. By treatment of a compound of formula S with a fluorinatingagent [for example KF or SbF₃] a 5-trifluoromethoxy-1,2,3-triazole offormula T may be prepared.

Oxidation of a compound of formula O with [for example sodium perborate]or treatment according to A. Sudalai et al. [Angew. Chem. Int. Ed. 40,405 (2001)] leads to a 5-nitro derivative of formula U. Alternatively, acompound of formula U may also be obtained by treatment of a compound offormula P or V with NaNO₂ in an polar solvent [such as DMF, sulpholaneor N-methylpyrrolidone] at elevated temperatures.

Transformations of a compound of formula (II′) [where R¹ and R² are asdefined in formula (I); Y is OR′; and R′ is C₁₋₅ alkyl] to give acompound of formula (II) [where R¹ and R² are as defined in formula (I)and Y is halo or hydroxy] includes saponification with a base [such asKOH or NaOH] in a protic solvent [such as methanol, ethanol or water],at ambient or elevated temperature to give a 1,2,3-triazole-4-carboxylicacid of formula W. Chlorination of a compound of formula W understandard conditions [for example with thionyl chloride, phosgene oroxalyl chloride] yields an acid chloride of formula Y.

Fluorination of a compound of formula W with DAST or SF₄ under mildconditions [low to ambient temperatures], preferably in an inert solvent[such as dichloromethane] gives an acid fluoride of formula Z.

(b) Preparation of a Compound of Formula (III).

A compound of formula (III)H₂N-A  (III)where A is as defined above for a compound of formula (I), is useful asan intermediate in the preparation of a compound of formula (I).

Most o-substituted amino-aryls and amino-heteroaryls of formula (III)are known from the literature, but some are novel.

A compound of formula (IIIa) may be obtained according to scheme 4:

Treatment of an orthlo-substituted nitrobenzonorbornadiene of formula AA(where R¹³, R¹⁴, R¹⁵, R¹⁶ and X are as defined above for a compound offormula (I)) [obtained through Diels-Alder addition of an in situgenerated benzyne, for example, starting from a 6-nitroanthranilic acidas described by L. Paquette et al, J. Amer. Chem. Soc. 99, 3734 (1977)or from other suitable benzyne precursers (see H. Pellissier et al.Tetrahedron, 59, 701 (2003) with a 5-7 membered cyclic 1,4-dieneaccording to, or by analogy to, L. Paquette et al, J. Amer. Chem. Soc.99, 3734 (1977), D. Gravel et al. Can. J. Chem. 69, 1193 (1991), J. R.Malpass et al. Tetrahedron, 48, 861 (1992), D. E. Lewis et al. SyntheticCommunications, 23, 993 (1993), R. N. Warrener et al. Molecules, 6, 353(2001), R. N. Warrener et al. Molecules, 6, 194 (2001) or I. Fleming etal. J. Chem. Soc., Perkin Trans.1, 2645 (1998)] with Zn, in the presenceof ammonium chloride or an aluminium amalgam, in a protic solvent [suchethanol or water] gives an aniline of formula CC, whilst catalytichydrogenation of a compound of formula AA with, for example, RaNi, Pd/Cor Rh/C in the presence of a solvent [for example THF, ethyl acetate,methanol or ethanol] affords an aniline of formula BB.

Compounds of formula (IIIb)

where R⁶ is an aliphatic or alicyclic, saturated or unsaturated group[in which the group contains three to thirteen carbon atoms and at leastone silicon atom and, optionally, one to three heteroatoms, eachindependently selected from oxygen, nitrogen and sulphur, and the groupis optionally substituted by up to four independently selected halogenatoms] and R⁷⁻¹⁰ are as defined in formula (I) may be prepared byanalogy with literature examples. References include e.g. E. A.Chemyshew et al., Bull. Acad. Sci. USSR, 1960, 1323; K. T. Kang et al.,Tetrahedron Letters, 32, 4341 (1991), Synthetic Comm., 24, 1507 (1994);M. Murata et al., Tetrahedron Letters 40, 9255 (1999); A. Falcou et al.,Tetrahedron 56, 225 (2000); A. Arcadi et al., Tetrahedron Letters 27,6397 (1986); K. C. Nicolaou et al., Chem. Eur. J. 1, 318 (1995); N.Chatani et al., J. Org. Chem. 60, 834 (1995); T. Stuedemann et al.,Tetrahedron 54, 1299 (1998); P. F. Hurdlik et al., J. Org. Chem. 54,5613 (1989); K. Karabelas et al., J. Org. Chem. 51, 5286 (1986); T.Jeffery, Tetrahedron Letters 40, 1673 (1999) and Tetrahedron Letters 41,8445 (2000); K. Olofson et al., J. Org. Chem. 63, 5076 (1998); H. Uirataet al., Bull. Chem. Soc. Jap. 57, 607 (1984); and G. Maas et al.,Tetrahedron 49, 881 (1983); and references cited therein.

Recent reviews for the introduction of Si-containing functionalitiesinto phenyl derivatives can be found in “The Chemistry of OrganosiliconCompounds”, Vols. 1-3, S. Patai, Z. Rappaport and Z. Rappaport, Y.Apeloid eds., Wiley 1989, 1998, 2001 and “Houben-Weyl Science andSynthesis”, Organometallics Vol. 4, I. Fleming ed., G. Thieme 2002.

Another group of anilines comprises compounds of formula (IIIc)

where R′ represents C₂₋₄ alkyl, C₂₋₄ haloalkyl or C₃₋₆ cycloalkyl(itself optionally substituted by up to 3 substituents, independentlyselected from halo, C₁₋₃ alkyl, C₁₋₃ haloalkyl and C₁₋₄ haloalkoxy).

A compound of formula (IIIc) may be prepared by a reaction sequencestarting with a crossed aldol condensation of benzaldehyde with a ketoneof formula CH₃C(O)R′ [where R′ is as defined above for a compound offormula (IIIc)] in the presence of NaOH or KOH in a solvent (such aswater or ethanol) and usually under reflux conditions or alternativelyby reaction of benzaldehyde with a Wittig reagent under standardconditions. The resulting α,β-unsaturated ketone of formula (IV) [whereR′ is as defined above for a compound (IIIc)]:

may then be converted into a compound of formula (V′) [where R′ is asdefined above for a compound (IIIc)]:

by reacting first with hydrazine hydrate in ethanol under refluxconditions and then heating (in the range of from 150 to 250° C.) in thepresence of KOH (distilling off the solvent). After nitration withHNO₃—H₂O or HNO₃-acetic anhydride in a cooled vessel (in the range offrom −30° C. to 0° C.), the resulting o/p-mixture of a nitrobenzene offormula (VI) [where R′ is as defined above for a compound (IIIc)]:

may then be separated and catalytically reduced (Pt/C/H₂ or Ra—Ni/H₂) ina solvent (such as methanol, ethanol of THF) at ambient temperature togive a compound of formula (IIIc).

Alternatively the synthesis of a compound of formula (IIId) [whereR′^(a) is hydrogen or methyl]

may be accomplished by a reaction sequence started by a Wittig reactionof o-nitrobenzaldehyde with an ylide, prepared from acyclopropylmethyltriphenylphosphonium bromide in the presence of astrong base [such as NaH] in a solvent [such as DMSO], in the range of0-85° C. The resulting E/Z-mixture of a compound of formula (VII)

[where R′^(a) is hydrogen or methyl] may be converted to a compound offormula (VIII)

by the application of the Simmons Smith reaction (Zn—Cu, CH₂I₂, ether asa solvent) to the olefin group of a compound of formula (VII) to give acompound of formula (VIII). The reduction of the nitro moiety of acompound of formula (VIII) to give a compound of formula (IIIc) may beperformed by using the same conditions as described above for a compoundof formula (VI).(c) Preparation of a Compound of Formula (I).

A compound of formula (I) [where A, R¹ and R² are as defined above andR³ is H] may be synthesized by reacting a compound of formula (II′)[where R¹ and R² are as defined above and R′ is C₁₋₅ alkyl] with ananiline of formula (III) [where A is as defined above for a compound offormula (I)] in the presence of NaN(TMS)₂ at −10° C. to ambienttemperature, preferably in dry THF, as described by J. Wang et al.,Synlett, 2001, 1485.

Alternatively, a compound of formula (I) [where A, R¹ and R² are asdefined above and R³ is H] may be prepared by reacting a compound offormula (II) [where R¹ and R² are as defined above and Y is OH] with acompound of formula (III) [where A is as defined above for a compound offormula (I)] in the presence of an activating agent [such as BOP-Cl] andtwo equivalents of a base [such as NEt₃] or by reacting a compound offormula (II) [where Y is Cl, Br or F] with a compound of formula (III)in the presence of one equivalent of a base [such as NEt₃, NaHCO₃,KHCO₃, Na₂CO₃ or K₂CO₃] in a solvent [such as dichloromethane, ethylacetate or DMF] preferably at −10 to 30° C.

A compound of formula (I) [where R³ is as defined above for formula (I),except that it is not hydrogen] may be prepared by reacting a compoundof formula (I) [where R³ is hydrogen] with a species Y—R³ [where R³ isas defined for formula (I), except that it is not hydrogen; and Y ishalogen, preferably Cl, Br or I; or Y is such that Y—R³ is an anhydride:that is, when R³ is COR*, Y is OCOR*] in the presence of a base [forexample NaH, NEt₃, NaHCO₃ or K₂CO₃] in an appropriate solvent [such asethyl acetate] or in a biphasic mixture [such as dichloromethane/watermixturte], at −10 to 30° C.

Surprisingly, it has now been found that the novel compounds of formula(I) have, for practical purposes, a very advantageous spectrum ofactivities for protecting plants against diseases that are caused byfungi as well as by bacteria and viruses.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use as active ingredients for controlling plant pests.The novel compounds are distinguished by excellent activity at low ratesof application, by being well tolerated by plants and by beingenvironmentally safe. They have very useful curative, preventive andsystemic properties and are used for protecting numerous cultivatedplants. The compounds of formula I can be used to inhibit or destroy thepests that occur on plants or parts of plants (fruit, blossoms, leaves,stems, tubers, roots) of different crops of useful plants, while at thesame time protecting also those parts of the plants that grow later, forexample from phytopathogenic microorganisms.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, in particular of seeds(fruit, tubers, grains) and plant cuttings (e.g. rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil.

Furthermore the compounds according to present invention may be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management, etc.

The compounds of formula (I) are, for example, effective against thephytopathogenic fungi of the following classes: Fungi imperfecti (e.g.Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercosporaand Altemaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia,Puccinia). Additionally, they are also effective against the Ascomycetesclasses (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula)and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).Outstanding activity has been observed against powdery mildew (Erysiphespp.). Furthermore, the novel compounds of formula I are effectiveagainst phytopathogenic bacteria and viruses (e.g. against Xanthomonasspp, Pseudomonas spp, Erwinia amylovora as well as against the tobaccomosaic virus).

Within the scope of present invention, target crops to be protectedtypically comprise the following species of plants: cereal (wheat,barley, rye, oat, rice, maize, sorghum and related species); beet (sugarbeet and fodder beet); pomes, drupes and soft fruit (apples, pears,plums, peaches, almonds, cherries, strawberries, raspberries andblackberries); leguminous plants (beans, lentils, peas, soybeans); oilplants (rape, mustard, poppy, olives, sunflowers, coconut, castor oilplants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges,lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus,cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae(avocado, cinnamomum, camphor) or plants such as tobacco, nuts, coffee,eggplants, sugar cane, tea, pepper, vines, hops, bananas and naturalrubber plants, as well as ornamentals.

The compounds of formula (I) are used in unmodified form or, preferably,together with the adjuvants conventionally employed in the art offormulation. To this end they are conveniently formulated in knownmanner to emulsifiable concentrates, coatable pastes, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts, granulates, and also encapsulations e.g. in polymericsubstances. As with the type of the compositions, the methods ofapplication, such as spraying, atomising, dusting, scattering, coatingor pouring, are chosen in accordance with the intended objectives andthe prevailing circumstances. The compositions may also contain furtheradjuvants such as stabilizers, antifoams, viscosity regulators, bindersor tackifiers as well as fertilizers, micronutrient donors or otherformulations for obtaining special effects.

Suitable carriers and adjuvants can be solid or liquid and aresubstances useful in formulation technology, e.g. natural or regeneratedmineral substances, solvents, dispersants, wetting agents, tackifiers,thickeners, binders or fertilizers. Such carriers are for exampledescribed in WO97/33890.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations which influence the growth of plants. They can also beselective herbicides as well as insecticides, fungicides, bactericides,nematicides, molluscicides or mixtures of several of these preparations,if desired together with further carriers, surfactants or applicationpromoting adjuvants customarily employed in the art of formulation.

The compounds of formula (I) can be mixed with other fungicides,resulting in some cases in unexpected synergistic activities. Mixingcomponents which are particularly preferred are azoles, such asazaconazole, BAY 14120, bitertanol, bromuconazole, cyproconazole,difenoconazole, diniconazole, epoxiconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil,imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate,penconazole, pyrifenox, prochloraz, propiconazole, simeconazole,tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole,triticonazole; pyrimidinyl carbinole, such as ancymidol, fenarimol,nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol,ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph,spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil,mepanipyrim, pyrimethanil; pyrroles, such as fenpiclonil, fludioxonil;phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl,ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim,debacarb, fuberidazole, thiabendazole; dicarboximides, such aschlozolinate, dichlozoline, iprodione, myclozoline, procymidone,vinclozoline; carboxamides, such as carboxin, fenfuram, flutolanil,mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine,dodine, iminoctadine; strobilurines, such as azoxystrobin,kresoxim-methyl, metominostrobin, SSF-129, trifloxystrobin,picoxystrobin, BAS 500F (proposed name pyraclostrobin), BAS 520;dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb,thiram, zineb, ziram; N-halomethylthiotetrahydrophthalimides, such ascaptafol, captan, dichlofluanid, fluoromides, folpet, tolyfluanid;Cu-compounds, such as Bordeaux mixture, copper hydroxide, copperoxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper;nitrophenol-derivatives, such as dinocap, nitrothal-isopropyl;organo-p-derivatives, such as edifenphos, iprobenphos, isoprothiolane,phosdiphen, pyrazophos, tolclofos-methyl; various others, such asacibenzolar-S-methyl, anilazine, benthiavalicarb, blasticidin-S,chinomethionate, chloroneb, chlorothalonil, cyflufenamid, cymoxanil,dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, SYP-LI90(proposed name: flumorph), dithianon, ethaboxam, etridiazole,famoxadone, fenamidone, fenoxanil, fentin, ferimzone, fluazinam,flusulfamide, fenhexamid, fosetyl-aluminium, hymexazol, iprovalicarb,IKF-916 (cyazofamid), kasugamycin, methasulfocarb, metrafenone,nicobifen, pencycuron, phthalide, polyoxins, probenazole, propamocarb,pyroquilon, quinoxyfen, quintozene, sulfur, triazoxide, tricyclazole,triforine, validamycin, zoxamide (RH7281).

A preferred method of applying a compound of formula (I), or anagrochemical composition which contains at least one of said compounds,is foliar application. The frequency of application and the rate ofapplication will depend on the risk of infestation by the correspondingpathogen. However, the compounds of formula I can also penetrate theplant through the roots via the soil (systemic action) by drenching thelocus of the plant with a liquid formulation, or by applying thecompounds in solid form to the soil, e.g. in granular form (soilapplication). In crops of water rice such granulates can be applied tothe flooded rice field. The compounds of formula I may also be appliedto seeds (coating) by impregnating the seeds or tubers either with aliquid formulation of the fungicide or coating them with a solidformulation.

A formulation [that is, a composition containing the compound of formula(I)] and, if desired, a solid or liquid adjuvant, is prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The agrochemical formulations will usually contain from 0.1 to 99% byweight, preferably from 0.1 to 95% by weight, of the compound of formulaI, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid orliquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25%by weight, of a surfactant.

Advantageous rates of application are normally from 5 g to 2 kg ofactive ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kga.i./ha, most preferably from 20 g to 600 g a.i./ha. When used as seeddrenching agent, convenient dosages are from 10 mg to 1 g of activesubstance per kg of seeds.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

The following non-limiting Examples illustrate the above-describedinvention in more detail.

EXAMPLE 1

This Example illustrates the preparation of Compound No. 1.15[2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methylester] and Compound No. 1.13[2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid].

a) Preparation of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic aciddimethylester and 1-methyl-1H-1,23-triazole-4,5-dicarboxylic aciddimethylester

1,2,3-Triazole-4,5-dicarboxylic acid dimethyl ester (Y. Tanaka et al.Tetrahedron 29, 3271 (1973)) (74.06 g; 0.40 mol), potassium carbonate(110.57 g; 0.80 mol) and methyl iodide (73.81 g; 0.52 mol) were reactedin acetonitrile (1000 ml) at 40° C. for 20 minutes and then for 20 hoursat ambient temperature. The mixture was poured onto ice-water andextracted with ether to give the crude product (70.66 g) as a mixture ofisomers. Separation on silica gel in ethyl acetate-hexane (2:3) yielded36.51 g (46%) of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic aciddimethylester [m.p. 86-87° C.; ¹H-NMR (300 MHz, DMSO-d₆), δ(ppm):4.27(s,3H), 3.88(s,6H)] and 26.92 g (34%) of1-methyl-1H-1,2,3-triazole-4,5-dicarboxylic dimethylester [m.p. 63-64°C.; ¹H-NMR (300 MHz, DMSO-d₆), δ(ppm): 4.19(s,3H), 3.93(s,3H),3.87(s,3H)].

b) Preparation of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic acidmonomethyl ester

To a solution of 2-methyl-2H-1,2,3-triazole-4,5-dicarboxylic aciddimethylester (1.2 g; 6 mmol) in 30 ml methanol was added 358 mg KOH(assay 86%; 5.5 mmol). The mixture was heated at reflux temperature for48 hours. The solvent was evaporated and the residue was then taken intowater and extracted with ethyl acetate (3 times). The combined organicphases contained non-reacted starting material. The aqueous phase wasacidified with 2N HCl (pH2-3) and extracted with ethyl acetate (3times). The extracts were combined, dried (anhydrous MgSO4) andevaporated to dryness to give 803 mg (72%) of the desired compound (m.p.125-126° C.; ¹H-NMR (300 MHz, DMSO-d₆), δ(ppm): 13.7(br.s,1H,exchangable with D₂O), 4.24(s,3H), 3.84(s,3H).

c) Preparation of2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methylester [Compound Number 1.15]

2-Methyl-2H-1,2,3-triazole-4,5-dicarboxylic acid monomethyl ester (2.9g; 15.66 mmol) and dichloromethane (160 ml) were placed in an 0.3 litremonel autoclave. Under an inert atmosphere and cooling with dry ice,gaseous HF (27 g) was introduced at −50° C. followed by gaseous SF₄(distilled, 6.9 g; 64.23 mmol). The autoclave was heated to 80° C. for 6hours. The maximum pressure amounted 9.8 bar. After cooling to ambienttemperature the reaction mixture was poured onto ice-dichloromethane andadjusted to pH7 with aqueous NaHCO₃. Extraction with dichloromethane (3times), drying over Na₂SO₄ and evaporation under reduced pressureafforded the crude product. Purification by Kugelrohr-distillation at 3mbar and ca. 180° C. gave 2.8 g (85%) of Compound No. 1.15 as ayellowish liquid.

¹H-NMR (300 MHz, CDCl₃), δ(ppm): 4.29(s,3H), 3.97(s,3H);

¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −61.7.

¹³C-NMR (125 MHz, CDCl₃), δ(ppm): 159.05, 139.65 (q, J_(C(5)F)=40.8 Hz),137.20, 119.63 (q, J_(CF)=269.4 Hz, CF₃), 52.96, 43.01.

d) Preparation of2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid [CompoundNumber 1.13]

A solution of 2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylicacid methyl ester [Compound Number 1.15] (2.09 g; 0.01 mol) and KOH(86%; 0.783 g; 1.2 eq.) in THF (50 ml) was heated at reflux temperaturefor 3.5 hours. The solution was evaporated, the residue was dissolved inwater and acidified to pH 1-2 with HCl (1M). Evaporation of the aqueoussolution followed by continuous extration in ethylacetate for 20 hoursgave of Compound No 1.13 (2.11 g; 100%) as a crystalline solid.

¹H-NMR (400 MHz, DMSO-d₆), δ(ppm): 4.19(s,3H).

¹⁹F-NMR (235 MHz, DMSO-d₆), δ (ppm): −59.3.

¹³C-NMR (125 MHz, DMSO-d₆), δ(ppm): 160.74, 144.08, 135.81 (q,J_(C(5)F)=38.1 Hz), 120.63 (q, J_(CF)=268.4 Hz, CF₃), 42.20.

EXAMPLE 2

This Example illustrates the preparation of Compound No. 1.03[2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methylester].

a) Preparation of5-Chlorocarbonyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methylester

Methyl 2-methyl-1,2,3-triazole-4,5-dicarboxylate (2.3 g; 0.011 mol) wasreacted with oxalyl chloride (1.46 ml; 0.014 mol) plus two drops of DMFin dichloromethane (20 ml) at 20° C. When the vigourous reaction ceasedthe temperature was raised to reflux for 15 hours. The mixture wasevaporated to dryness to give 2.7 g of the acid chloride as a solid.¹H-NMR (300 MHz, CDCl₃), δ (ppm): 4.48(s, H), 4.0(s,3H).

b) Preparation of 5-formyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acidmethyl ester

To a solution of freshly prepared5-Chlorocarbonyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methylester (2.7 g; ca. 13 mmol) in THF (270 ml) was addedethyl-diisopropyl-amine (1.88 g; 1.1 eq.). The mixture was hydrogenatedin the presence of 2.7 g 10% Pd/C at 0-5° C. at normal pressure for 2½hours and subsequently filtered from the catalyst. The clear solutionwas evaporated to give the crude as a solid which was dissolved again inethyl acetate and stirred for a couple of minutes with silica gel. Afterfiltration and evaporation 1.77 g (84%) of pure product as off-whitecrystals were obtained [m.p. 107-108° C.; ¹H-NMR (300 MHz, CDCl₃), δ(ppm): 10.43(s,1H), 4.33(s,3H), 4.01(s,3H)].

c) Preparation of2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methylester. [Compound No. 1.03.]

5-Formyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methyl ester (600mg; 3.5 mmol) in 0.5 ml CHCl₃ were reacted with(bis(2-methoxyethyl)amino)sulfurtrifluoride (1350 mg; 6.1 mmol) atambient temperature to 50° C. for 6 days. The resulting orange solutionwas carefully quenched with 6 ml of a saturated aqueous NaHCO₃ solution(vigorous reaction) and extracted with ethyl acetate (twice). Thecombined organic phases were washed with aqueous NaHCO₃-solution, driedover anhydrous MgSO₄ and evaporated to give 351 mg (52%) of colourlesscrystals.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 7.15(t, J_(HF)=53.5 Hz, 1H, H—CF₂),4.30(s,3H), 3.98(s,3H); ¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −116.1;¹³C-NMR (125 MHz, CDCl₃), δ (ppm): 160.0, 143.6(t, J_(C(5)F)=25.6 Hz),137.2, 108.0(t, J_((CF))=237.8 Hz, CHF₂), 52.6, 42.7].

EXAMPLE 3

This Example illustrates the preparation of Compound No. 1.50[2-methyl-5-fluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methylester].

a) Preparation of5-hydroxymethyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid methylester

2.6 g (13.3 mmol) of 5-formyl-2-methyl-2H-1,2,3-triazole-4-carboxylicacid methyl ester (see Example 2a) in methanol (100 ml) was treated withNaBH₄ (601 mg) under stirring for 1 hour at ambient temperature. Thereaction mixture was quenched with saturated aqueous ammonium chloridesolution, extracted with ethyl acetate, dried with Na₂SO₄ and evaporatedto give the crude as an oil. Purification on silica gel in ethylacetate:hexane (2:1) yielded 1.85 g (81%) of the crystalline product,m.p. 112-113° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 4.86(d, J=6.9 Hz, 1H), 4.22(s,3H),3.98(s,3H), 3.53(t; J=6.9 Hz, exchangeable with D₂O).

b) Preparation of 2-methyl-5-fluoromethyl-2H-1,2,3-triazole-5-carboxylicacid methyl ester. [Compound No. 1.50.]

A solution of 5-hydroxymethyl-2-methyl-2H-1,2,3-triazole-4-carboxylicacid methyl ester (200 mg; 1.1 mmol) in CH₂Cl₂ (15 ml) was reacted with0.26 ml diethylamino sulfur trifluoride (2 mmol) for 15 minutes at −40°C. followed by 15 hours at ambient temperature. After evaporation, thecrude product was purified on silica gel in ethyl acetate:hexane (3:1)to give 181 mg (95%) of the desired product, m.p. 64-66° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 5.66(d, J_(HF)=47.5 Hz, 2H, H₂—CF),4.26(s,3H), 3.96(s,3H).

¹⁹F-NMR (235 MHz, CDCl₃), δ (ppm): −214.

¹³C-NMR (125 MHz, CDCl₃), δ (ppm): 161.6, 145.86 (d, J_(C(5)F)=18.7 Hz),137.09, 74.82(d, J_(CF)=166.6 Hz, CH₂F), 52.2, 42.3.

EXAMPLE 4

This Example illustrates the preparation of Compound No. 3.017[5-difluoromethyl-2-methyl-2H-1,2,3-triazole-4-carboxylic acid(4′-chloro-biphenyl-2-yl)-amide].

To a solution of2-methyl-5-difluoromethyl-2H-1,2,3-triazole-5-carboxylic acid methylester (300 mg; 1.57 mmol) and 4′-chloro-biphenyl-2-ylamine (320 mg; 1.57mmol) in THF (3 ml) was added sodium bis(trimethylsilyl)-amide (0.88 ml2M in THF; 1.76 mmol; 1.12 eq.) by syringe at 0° C. over 1.5 minutes.The reaction mixture was stirred at 0° C. for 15 minutes and then atambient temperature for 22 hours. It was then poured on cold saturatedNH₄Cl solution and extracted with ethyl acetate. After washing withbrine it was dried (anhydrous MgSO₄) and evaporated to dryness to give asolid, which was triturated with hexane. The colourless crystallineproduct was filtered and dried: 300 mg (53%) [m.p. 155-156° C.; 1H-NMR(300 MHz, CDCl₃), δ (ppm): 8.5(br, exchangeable with D₂O, 1H), 8.4 (d,1H), 7.5-7.2(m,7H), 7.38 (t, J_(HF)=52.5 Hz, 1H, CHF₂), 4.2(s,3H),LC-MS: 363(M+H)].

EXAMPLE 5

This Example illustrates the preparation of Compound No. 2.219[2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid[2-(1,3-dimethyl-butyl)-phenyl]-amide].

To a solution of2-methyl-5-trifluoromethyl-2H-1,2,3-triazole-4-carboxylic acid methylester (1150 mg; 0.75 mmol) and 2-(1,3-dimethyl-butyl)-phenylamine (133mg; 0.75 mmol) in 1.5 ml THF was added sodium bis(trimethylsilyl)-amide(0.638 ml 2M in THF; 1.7 eq.) by syringe at ambient temperature. Thereaction mixture was stirred for 20 hours and was then poured on coldsaturated NH₄Cl solution and extracted with ethyl acetate. After washingwith brine it was dried (anhydrous MgSO₄) and evaporated to dryness togive the crude product, which was purified on silica gel incyclohexane-ethyl acetate (18:1) The crystalline product was trituratedin hexane, filtered and dried in vacuo to yield 130 mg (49%) of CompoundNo. 2.219 [mp 94.6-95.4° C.; 1H-NMR (300 MHz, CDCl₃), δ (ppm): 8.5(br.s,exchangeable with D₂O,1H), 8.0(d,1H), 7.3-7.15(m,3H), 4.33(s,3H),3.0(m,1H), 1.55-1.35(m,3H), 1.26(d,3H), 0.9(2d,6H); LC-MS: 355.6(M+H)].

EXAMPLE 6

This Example illustrates the preparation of Compound No. 26.014[1,8-Dimethyl-11-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6-trien-3-yl-amine].

A solution of 1,4-dimethyl-5-nitro-1,4-dihydro-1,4-epoxynaphthalene(5.49 g; 25.27 mmol) (see T. Nishiyama et al., Rikagaku-hen, 28, 37-43(2000)) in 55 ml THF was hydrogenated in the presence of RaNi (1.1 g) atambient temparature. Hydrogen uptake was 2.23 litre (97%) after 18hours. After filtering off the catalyst, the filtrate was evaporated andtaken into ether, washed with aqueous NaHCO₃-solution and dried (NaSO₄)to give 4.60 g of crude product, as an oil. Trituration with hexane anda trace of ether furnished a total of 4.5 g (94%) of reddish crystallineproduct, m.p. 92-93° C.

¹H-NMR (300 MHz, CDCl₃), δ (ppm): 7.05(t,1H), 6.7(t,2H), ca.5(br.,exchangeable with D₂O, 2H), 2.0(s,3H), 1.9(m,2H), 1.8(s,3H), 1.7(m,1H),1.5(m,1H).

EXAMPLE 7

This Example illustrates the preparation of Compound No. 26.001[1,8-Dimethyl-11-oxa-tricyclo[6.2.1.0*2.7*]undeca-2,4,6,9-tetraen-3-yl-anine].

To 1,4-dimethyl-5-nitro-1,4-dihydro-1,4-epoxynaphthalene (4.22 g; 19.43mmol) (see Example 6) in ethanol (60 ml) was added a solution ofammoniumchloride (2.08 g) in H₂O (5.2 ml) at 47° C. Under vigorousstirring, zinc powder (9.10 g; 0.14 mol) was added in portions over aperiod of 5 minutes. The suspension was heated to reflux for 5½ hoursfollowed by filtration through Hyflo™ to give a clear yellow filtrate.After evaporation, the crude product amounted 4.57 g, as a viscous oil.Column chromatography on silica gel in ethyl acetate-hexane (1:4) gave1.24 g (34%) of the desired product, as brownish crystals, m.p. 92-96°C.

¹H-NMR (300 MHz, CDCl₃), δ(ppm): 6.85 and 6.7(two m, 2×2H), 6.47(t,1H),ca.5-3 (br., exchangeable with D₂O,2H), 2.07(s,3H), 1.85(s,3H).

FORMULATION EXAMPLES FOR COMPOUNDS OF FORMULA (I)

Working procedures for preparing formulations of the compounds offormula I such as Emulsifiable Concentrates, Solutions, Granules, Dustsand Wettable Powders are described in WO97/33890.

BIOLOGICAL EXAMPLES FUNGICIDAL ACTIONS Example B-1 Action AgainstPuccinia recondita/Wheat (Brownrust on Wheat)

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (1×10⁵ uredospores/ml) on the test plants. After anincubation period of 2 days at 20° C. and 95% r.h. the plants are keptin a greenhouse for 8 days at 20° C. and 60% r.h. The disease incidenceis assessed 10 days after inoculation.

Infestation is prevented virtually completely (0-5% infestation) witheach of Compounds 2.273, 3.219, 3.273, 3.321, 8.189, 9.189, 20.017,20.022, 21.017 and 21.022.

Example B-2 Action Against Podosphaera leucotricha/Apple (Powdery Mildewon Apple)

5 week old apple seedlings cv. McIntosh are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter, the application apple plants are inoculated by shaking plantsinfected with apple powdery mildew above the test plants. After anincubation period of 12 days at 22° C. and 60% r.h. under a light regimeof 14/10 hours (light/dark) the disease incidence is assessed.

Compounds 2.005, 3.017, 3.219 and 9.189 each exhibit strong efficacy(<20% infestation).

Example B-3 Action Against Venturia inaegualis/Apple (Scab on Apple)

4 week old apple seedlings cv. McIntosh are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the apple plants are inoculated by spraying a sporesuspension (4×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 21° C. and 95% r.h. the plants are placed for 4 daysat 21° C. and 60% r.h. in a greenhouse. After another 4 day incubationperiod at 21° C. and 95% r.h. the disease incidence is assessed.

Compounds 3.017, 3.219 and 9.189 each exhibit strong efficacy (<20%infestation).

Example B-4 Action against Erysiphe graminis/Barley (Powdery Mildew onBarley)

1 week old barley plants cv. Regina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the barley plants are inoculated by shaking powdery mildewinfected plants above the test plants. After an incubation period of 6days at 20° C./18° C. (day/night) and 60% r.h. in a greenhouse thedisease incidence is assessed.

Compounds 2.017, 2.029, 2.273, 3.005, 3.017, 3.029, 3.067, 3.070, 3.219,3.273, 3.321, 3.407, 8.189, 9.189 and 21.017 each exhibit strongefficacy (<20% infestation).

Example B-5 Action Against Botrytis cinerea/Grape (Botrytis on Gapes)

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the grape plants are inoculated by spraying a sporesuspension (1×10⁶ conidia/ml) on the test plants. After an incubationperiod of 4 days at 21° C. and 95% r.h. in a greenhouse the diseaseincidence is assessed.

Compounds 2.029, 3.017 and 3.219 each show good activity in this test(<50% disease incidence).

Example B-6 Action Against Botrytis cinerea/Tomato (Botrytis onTomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (1×10⁵ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed.

Compounds 2.029, 3.005, 3.029, 3.067, 3.070, 3.219, 3.273, 9.189 and20.017 each exhibit good efficacy (<50% disease incidence).

Example B-7 Action Against Seotoria nodorum/Wheat (Septoria Leaf Spot onWheat)

1 week old wheat plants cv. Arina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. One day afterapplication, the wheat plants are inoculated by spraying a sporesuspension (5×10⁵ conidia/ml) on the test plants. After an incubationperiod of 1 day at 20° C. and 95% r.h. the plants are kept for 10 daysat 20° C. and 60% r.h. in a greenhouse. The disease incidence isassessed 11 days after inoculation.

Compounds 3.273 and 9.189 each show good activity in this test (<50%disease incidence).

Example B-8 Action Against Helminthosporium teres/Barley (Net Blotch onBarley

1 week old barley plants cv. Regina are treated with the formulated testcompound (0.02% active ingredient) in a spray chamber. Two days afterapplication, the barley plants are inoculated by spraying a sporesuspension (3×10⁴ conidia/ml) on the test plants. After an incubationperiod of 4 days at 20° C. and 95% r.h. in a greenhouse the diseaseincidence is assessed.

Compounds 2.005, 2.017, 2.029, 2.067, 2.070, 2.273, 3.005, 3.017, 3.029,3.067, 3.070, 3.219, 3.407, 9.189 and 21.017 each show good activity inthis test (<20% disease incidence).

Example B-9 Action Against Altemaria solani/Tomato (Early Blight onTomatoes)

4 week old tomato plants cv. Roter Gnom are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. Two daysafter application, the tomato plants are inoculated by spraying a sporesuspension (2×10⁵ conidia/ml) on the test plants. After an incubationperiod of 3 days at 20° C. and 95% r.h. in a growth chamber the diseaseincidence is assessed.

Compounds 2.005, 2.029, 3.005, 3.017, 3.029 and 9.189 each show goodactivity in this test (<20% disease incidence).

Example B-10 Action Against Uncinula necator/Grape (Powdery Mildew onGapes)

5 week old grape seedlings cv. Gutedel are treated with the formulatedtest compound (0.02% active ingredient) in a spray chamber. One dayafter application, the grape plants are inoculated by shaking plantsinfected with grape powdery mildew above the test plants. After anincubation period of 7 days at 26° C. and 60% r.h. under a light regimeof 14/10 hours (light/dark) the disease incidence is assessed.

Compounds 3.017, 3.219 and 9.189 each show good activity in this test(<20% disease incidence).

1. A compound of formula (I):

where A is an ortho-substituted ring selected from formulae (A1) to(A22);

Q is a single or a double bond; X is O, N(R¹⁸), S orCR¹⁹R²⁰)(CR²¹R²²)_(m)(CR²³R²⁴)_(n); R¹ is halogen, cyano, nitro, C₁₋₄alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy or optionallysubstituted C₂₋₄ alkenyl, optionally substituted C₂₋₄ alkynyl oroptionally substituted SO₂(C₁₋₄)alkyl (where the optionally substitutedmoieties may each have up to 3 substituents, each independently selectedfrom halogen and C₁₋₄alkoxy); R² is C₁₋₄alkyl, C₁₋₄ haloalkyl, C₁₋₄alkoxy(C₁₋₄)alkyl or C₁₋₄ alkylthio(C₁₋₄)alkyl or optionally substitutedaryl (C₁₋₄)alkyl- or [optionally substituted aryl]oxy(C₁₋₄)alkyl- (wherethe optionally substituted aryl moieties may each have up to 3substituents, each independently selected from halogen and C₁₋₄ alkoxy);R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ or COR⁵ or optionallysubstituted C₁₋₄alkyl, optionally substituted C₁₋₄ alkoxy or optionallysubstituted (C₁₋₄)alkylC(═O)O (where the optionally substituted moietiesmay each have up to 3 substituents, each independently selected fromhalogen, C₁₋₄alkoxy, C₁₋₄ alkyl, C₁₋₂ haloalkoxy, hydroxy, cyano,carboxyl, methoxycarbonyl, ethoxycarbonyl, methylsulfonyl andethylsulfonyl); each R⁴ is, independently, hydrogen, halogen, C₁₋₄alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy or C₁₋₄ alkoxy(C₁₋₄)alkyl; R⁵ ishydrogen or optionally substituted C₁₋₆ alkyl, optionally substitutedC₁₋₄ alkoxy, optionally substituted C₁₋₄ alkoxy(C₁₋₄)alkyl, optionallysubstituted C₁₋₄ alkylthio(C₁₋₄)alkyl or optionally substituted aryl(where the optionally substituted moieties may each have up to 3substituents, each independently selected from halogen, C₁₋₆ alkoxy,C₁₋₆ haloalkoxy, cyano, hydroxy, methoxycarbonyl and ethoxycarbonyl); R⁶is i) phenyl optionally substituted by up to 3 substituents, eachindependently selected from halogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ haloalkylthio, C(H)═N—OH,C(H)═N—O(C₁₋₆ alkyl), C(C₁₋₆ alkyl)═N—OH, C(C₁₋₆ alkyl)═N—O—(C₁₋₆alkyl), (Z)pC≡CR₂₅ and (Z)pCR₂₈═CR₂₆R₂₇; ii) a 5-6 membered heterocyclicring in which the ring contains 1 to 3 heteroatoms (each independentlychosen from oxygen, sulphur and nitrogen) and the ring is optionallysubstituted by up to 3 substituents, each independently selected fromhalogen, cyano, nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄haloalkoxy, C(H)═N—O—(C₁₋₆ alkyl) and C(C₁₋₆ alkyl)cyano, C₁₋₄ alkoxy,C₁₋₄ thioalkyl, COO—C₁₋₄ alkyl, ═N—OH, ═N—O—(C₁-4 alkyl), C₃₋₈cycloalkyl (itself optionally substituted by up to 3 substituents, eachindependently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄haloalkoxy) and C₄₋₈ cycloalkenyl (itself optionally substituted by upto 3 substituents, each independently selected from C₁₋₄ alkyl, halogen,C₁₋₄ alkoxy and C₁₋₄ haloalkoxy); iii) C₂₋₁₂ alkenyl optionallysubstituted by up to 6 substituents, each independently selected fromhalogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—(C₁₋₄ alkyl), ═N—OH,═N—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionally substituted by upto 3 substituents, each independently selected from C₁₋₄ alkyl, halogen,C₁₋₄alkoxy and C₁₋₄ haloalkoxy) and C₄₋₈ cycloalkenyl (itself optionallysubstituted by up to 3 substituents, each independently selected fromC₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy); iv) C₂₋₁₂ alkynyloptionally substituted by up to 6 substituents, each independentlyselected from halogen, cyano, C₁₋₄ alkoxy, C₁₋₄ thioalkyl, COO—C₁₋₄alkyl, ═N—OH, ═H—O—(C₁₋₄ alkyl), C₃₋₈ cycloalkyl (itself optionallysubstituted by up to 3 substituents, each independently selected fromC₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄ haloalkoxy), Si(CH₃)₃ and C₄₋₈cycloalkenyl (itself optionally substituted by up to 3 substituents,each independently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy andC₁₋₄ haloalkoxy); v) C₃₋₈ cycloalkyl optionally substituted by up to 3substituents, each independently selected from halogen, C₁₋₄ alkyl, C₁₋₄haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₃₋₆ cycloalkyl(itself optionally substituted by up to 3 substituents, eachindependently selected from C₁₋₄ alkyl, halogen, C₁₋₄ alkoxy and C₁₋₄haloalkoxy) and phenyl (itself optionally substituted by up to fiveindependently selected halogen atoms); vi) C₄₋₈ cycloalkenyl optionallysubstituted by up to 3 substituents, each independently selected fromhalogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄thioalkyl, C₃₋₆ cycloalkyl (itself optionally substituted by up to 3substituents, each independently selected from C₁₋₄ alkyl, halogen,C₁₋₄alkoxy and C₁₋₄ haloalkoxy) and phenyl (itself optionallysubstituted by up to five independently selected halogen atoms); vii)C₆₋₁₂ bicycloalkyl optionally substituted by up to 3 substituents, eachindependently selected from halogen, C₁₋₄ alkyl and C₁₋₄ haloalkyl; orviii) an aliphatic, saturated or unsaturated group in which the groupcontains three to thirteen carbon atoms and at least one silicon atomand, optionally, one to three heteroatoms, each independently selectedfrom oxygen, nitrogen and sulphur, and the group is optionallysubstituted by up to four independently selected halogen atoms; R⁷, R⁸,R⁹, R¹⁰, R¹¹ and R¹² are each, independently, hydrogen, halogen, cyano,nitro, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄thioalkyl or C₁₋₄ thiohaloalkyl; R¹³, R¹⁴, R¹⁵, R¹⁶ and R¹⁷ are each,independently, hydrogen, halogen, C₁₋₄ alkyl, C(O)CH₃, C₁₋₄ haloalkyl,C₁₋₄ alkoxy, C₁₋₄ haloalkoxy, C₁₋₄ thioalkyl, C₁₋₄ thiohaloalkyl,hydroxymethyl or C₁₋ alkoxymethyl; R¹⁸ is hydrogen, C₁₋₄ alkyl, C₁₋₄alkoxy(C₁₋₄)alkyl, formyl, C(═O)C₁₋₄alkyl (optionally substituted byhalogen or C₁₋₄ alkoxy) or C(═O)O—C₁₋₆ alkyl (optionally substituted byhalogen, C₁₋₄ alkoxy or CN); R¹⁹, R²⁰, R²¹, R²², R²³ and R²⁴ are each,independently, C₁₋₆ alkyl, C₁₋₆ alkenyl both optionally substituted byhalogen, hydroxy, ═O, C₁₋₄ alkoxy, O—C(O)—C₁₋₄ alkyl, aryl or a 3-7membered carbocyclic ring (itself optionally substituted by up to threemethyl groups), a 3-7 membered carbocyclic ring (optionally substitutedby up to three methyl groups and optionally containing one heteroatomselected from nitrogen and oxygen), hydrogen, halogen, hydroxy or C₁₋₄alkoxy; or R¹⁹R²⁰ together with the carbon atom to which they areattached form a carbonyl-group, a 3-5 membered carbocyclic ring(optionally substituted by up to three methyl groups), C₁₋₆ alkylidene(optionally substituted by up to three methyl groups) or C₃₋₆cycloalkylidene (optionally substituted by up to three methyl groups);R²⁵ is hydrogen, halogen, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄alkoxy(C₁₋₄)alkyl, C₁₋₄ haloalkoxy(C₁₋₄)alkyl or Si(C₁₋₄ alkyl)₃; R²⁶and R²⁷ are each, independently, hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄haloalkyl; R²⁸ is hydrogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl; m is 0 or 1; nis 0 or 1; p is 0 or 1; and Z is C₁₋₄ alkylene.
 2. A compound of formula(I) according to claim 1, where A is selected from formulae (A1), (A2),(A3), (A16), (A17), (A18), (A19), (A20) and (A22).
 3. A compound offormula (I) according to claim 1, where R¹ is C₁₋₄ alkyl, C₁₋₄haloalkyl, NO₂, CN or OCF₃.
 4. A compound of formula (I) according toclaim 1, where R² is C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ alkoxy(C₁₋₄)alkylor C₁₋₄ alkylthio(C₁₋₄)alkyl.
 5. A compound of formula (I) according toclaim 1, where R³ is hydrogen, CH₂C≡CR⁴, CH₂CR⁴═C(H)R⁴, CH═C═CH₂ orCOR⁵.
 6. A composition comprising a compound of formula (I) according toclaim 1, together with a suitable carrier.
 7. A method of controlling orpreventing infestation of cultivated plants by fungi by application of acompound of formula (I) according to claim 1, to plants, to partsthereof or the locus thereof.